Muon hyperfine constants A_μ have been measured by transverse field μSR for (CH3)3Si\mbox\.CHMu in hexane from 167 K to 332 K. In addition, avoided level‐crossing resonance was used to determine \alpha‐proton coupling constants Ap over a similar range of temperatures. The two hyperfine constants can be described by a common temperature dependence, d|Ai|/ dT=1.4\times 10-3 MHz\,K-1, where Ai represents Ap or the reduced muon constant A^\prime_μ=0.3141A_μ. There is a small isotope effect (A^\prime_μ is 2.2 % larger than Ap) consistent with zero‐point motion in the anharmonic C–H bond stretch. The common temperature dependence is tentatively attributed to a coupled deviation of the C–H and C–Mu bonds out of the nodal plane of the p orbital containing the unpaired electron.
