Potassium tert-amylate ( t-AmylOK) is a well-known, commercially available base and generally regarded as a more solvent-soluble form of potassium tert-butoxide ( t-BuOK). However, despite the structural similarity between the tert-butyl and amyl moieties, potassium tert-amylate in toluene can undergo distinct physical property changes in the presence of protic solvents that warrant further consideration. This is particularly surprising given that t-AmylOH is a byproduct of deprotonation with t-AmylOK, as well as the fact that its structurally similar relative, t-BuOK, is commercially available in t-BuOH.