Decoherence represents a double-edged sword for pulsed electron paramagnetic resonance (EPR) as this process limits the achievable resolution and/or sensitivity of an experiment but also reports on the decoherence-inducing spin environment. For this reason, the manipulation and understanding of underlying decoherence mechanisms is pivotal. Pulsed manipulation by n refocusing pulses, i.e. dynamical decoupling (DD), is known since the introduction of the Carr-Purcell (CP) sequence to prolong the phase-memory time Tm. This concept has been integrated into pulsed dipolar spectroscopy sequences to accesses longer distances. Instead, EPR spectroscopists conventionally rely on only the Hahn (n = 1) experiment to observe decoherence and assess the driving mechanism based on a Tm and a stretch parameter ξ that together model the associated echo envelope decay. This thesis explores DD for EPR spectroscopy by applying the CP and Uhrig n = 1-5 sequences to relevant spin systems for chemical and biological EPR application work, namely spin labels in the glassy, frozen state. Besides extending the decoherence process, the presented work demonstrates that DD is a spectroscopic method in itself: compared to the conventional Hahn-based approach it is superior in analyzing and quantitatively describing the decoherence process of transverse electronic relaxation. Part I reports the acquired DD data sets including a stretch exponential(s) parameterization. The scaling of Tm and ξ with n provides a convenient framework to identify and discuss contributing decoherence mechanisms. Part II introduces regularized noise spectroscopy to infer the so-called noise spectrum from DD data. Unlike Tm and ξ parameters, this quantitative decoherence descriptor is far more comprehensive as it captures the fluctuating spin environment and rationalizes the observed DD performance. The focus lies on the low-temperature and low spin-concentration regime as these optimized experimental conditions achieve the largest DD gain by freezing out decoherence-inducing dynamics and limiting non-refocusable interactions between electron spins. DD experiments with nitroxides in o-terphenyl (OTP) and water-glycerol reveal a fast and a slow decoherence pathway, assigned by means of deuteration to the geminal methyl groups of the nitroxide and solvent nuclei, respectively. Mechanistically, nuclear spin diffusion (NSD) drives the latter process, whereas the observed methyl deuteration effect suggests rotational tunneling, affirmed by simulations. In absence of methyl groups, as is the case for the studied trityl radicals, a reduced NSD-driven coherence loss to intramolecular nuclei is observed. DD refocuses all these nuclear spin-induced decoherence mechanisms thereby linearly extending the associated Tm with n, yet with varying efficiency. Compared to the intramolecular nuclei of nitroxides and trityl radicals, the flip-flop transitions of solvent nuclei generate relatively slowly fluctuating hyperfine fields, producing noise spectral features that extend up to a cut-off frequency of νc = 40-100 kHz. This value is generally larger for protonated solvents, implying a stronger weighting of low-frequency contributions. As the Uhrig sequence is optimized to suppress this type of fluctuations, it outperforms the CP scheme in case of protonated matrices. Solvent deuteration reduces νc, reporting on slower nuclear bath dynamics on a time scale tc = 1/νc, that DD more effectively suppresses, producing a steeper Tm/n slope. In contrast, repeated refocusing cannot alleviate zero field splitting (ZFS)-induced coherence losses. Applying DD to gadolinium complexes in water-glycerol thus identifies the relative contribution arising from the associated transient ZFS mechanism and solvent-driven NSD. Unlike for spin labels in OTP or water-glycerol, for a nitroxide-labeled peptide embedded in a lipid bilayer, a single, fast decoherence process is observed, featuring a Tm increase that saturates with n. Though lipid deuteration extends Tm it does not reduce the noise spectral width, thus reflecting a much smaller deuteration effect compared to OTP and water-glycerol. As the only one of all studied spin environments, the ξ dependence on n exhibits for deuterated lipids an even-odd pulse parity. From this property, a lower limit of the nuclear flip-flop time can be estimated that is significantly shorter than tc of OTP and water-glycerol. This rapidly fluctuating lipid spin environment hence constitutes a DD limit, explaining the saturating refocusing effect. In summary, this thesis utilizes DD to address the double relevance of decoherence for pulsed EPR spectroscopy. First, DD extends Tm and thus serves as a resolution- and/or sensitivity-enhancing building block, second, DD enables a comprehensive analysis of the underlying decoherence mechanisms. By introducing regularized noise spectroscopy, the presented work provides the connecting link between the understanding and rational manipulation of the decoherence process. The author hopes that the noise spectrum as a quantitative decoherence descriptor resonates with the EPR community and will find widespread application.