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Long electron spin coherence lifetimes are crucial for high sensitivity and resolution in many pulse electron paramagnetic resonance (EPR) experiments aimed at measuring hyperfine and dipolar couplings, as well as in potential quantum sensing applications of molecular spin qubits. In immobilized systems, methyl groups contribute significantly to electron spin decoherence as a result of methyl torsional quantum tunneling. We examine the electron spin decoherence dynamics of the nitroxide radical 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) in both a methyl-free solvent and a methyl-containing solvent at cryogenic temperature. We model nitroxide and solvent methyl effects on decoherence using cluster correlation expansion (CCE) simulations extended to include methyl tunneling and compare the calculations to experimental data. We show that by using the methyl tunneling frequency as a fit parameter, experimental Hahn echo decays can be reproduced fairly well, allowing structural properties to be investigated in silico. In addition, we examine the Hahn echo of a hypothetical system with an unpaired electron and a single methyl to determine the effect of geometric configuration on methyl-driven electron spin decoherence. The simulations show that a methyl group contributes the most to electron spin decoherence if it is located between 2.5 and 6–7 Å from the electron spin, with its orientation being of secondary importance.