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We examine networks of complementary-DNA-strand cross-linked polyacrylamide, with and without covalent N,N′-methylene(bis)acrylamide cross-linking, using rheological time–temperature superposition (TTS) to ascertain how temperature and composition influence the microstructure. A higher DNA-cross-linking efficiency is ascribed to the larger cross-linker imparting greater steric hindrance to the formation of self-terminating loops. TTS unifies the rheological spectra of DNA cross-linked and dual cross-linked gels at low frequencies, furnishing the effective activation energy for DNA-cross-link disengagement. Temperature sweeps also show that the temperature dependence of the dynamic moduli is reversible. The activation energy is temperature-independent (≈318 kJ mol–1) at low temperatures but decreases significantly and systematically with increasing temperature (and varying cross-linker composition). We interpret the varying activation energy—relative to the low-temperature limit—as a measure of DNA-cross-linker disassociation, and infer from TTS a cooperative relationship between the DNA-cross-linker disengagement and network connectivity. At low temperature, DNA cross-linked samples exhibit hallmarks of star-polymer-melt relaxation, including a superexponential divergence of the longest relaxation time with increasing cross-linker concentration, increasing from ≈2 to 20 entanglements per arm. At high temperature, a new “associative-reptation” scaling furnishes a robust interpretation of the network and longest relaxation times.