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Double-imaging photoelectron/photoion coincidence (i²PEPICO) spectroscopy using a multiplexing, time-efficient, fixed-photon-energy approach offers important opportunities of gas-phase analysis. Building on successful applications in combustion systems that have demonstrated the discriminative power of this technique, we attempt here to push the limits of its application further to more chemically complex combustion examples. The present investigation is devoted to identifying and potentially quantifying compounds featuring five heavy atoms in laminar, premixed low-pressure flames of hydrocarbon and oxygenated fuels and their mixtures. In these combustion examples from flames of cyclopentene, iso-pentane, iso-pentane blended with dimethyl ether (DME), and diethyl ether (DEE), we focus on the unambiguous assignment and quantitative detection of species with the sum formulae C5H6, C5H7, C5H8, C5H10, and C4H8O in the respective isomer mixtures, attempting to provide answers to specific chemical questions for each of these examples. To analyze the obtained i2PEPICO results from these combustion situations, photoelectron spectra (PES) from pure reference compounds, including several examples previously unavailable in the literature, were recorded with the same experimental setup as used in the flame measurements. In addition, PES of two species where reference spectra have not been obtained, namely 2-methyl-1-butene (C5H10) and the 2-cyclopentenyl radical (C5H7), were calculated on the basis of high-level ab initio calculations and Franck-Condon (FC) simulations. These reference measurements and quantum chemical calculations support the early fuel decomposition scheme in the cyclopentene flame towards 2-cyclopentenyl as the dominant fuel radical as well as the prevalence of branched intermediates in the early fuel destruction reactions in the iso-pentane flame, with only minor influences from DME addition. Furthermore, the presence of ethyl vinyl ether (EVE) in DEE flames that was predicted by a recent DEE combustion mechanism could be confirmed unambiguously. While combustion measurements using i2PEPICO can be readily obtained in isomer-rich situations, we wish to highlight the crucial need for high-quality reference information to assign and evaluate the obtained spectra. [ABSTRACT FROM AUTHOR]