Spin specificity is one of the most important properties of carbenes in their reactions. Alcohols are typically used to probe the reactive spin states of carbenes: OH insertions are assumed to be characteristic of singlet states, whereas CH insertions are typical for the triplets. Surprisingly, the experiments presented here suggest that the spin ground state of diphenylcarbene 1 switches from triplet to singlet if the carbene is allowed to interact with methanol. Carbene 1 and methanol form a strongly hydrogen-bonded singlet ground state complex that was synthesized in low-temperature matrices and characterized by IR spectroscopy. This methanol complex is only metastable, and even at 3 K slowly rearranges to form the product of OH insertion through quantum chemical tunneling. Thus, the ground state triplet (in the gas phase) carbene 1 forms exclusively the products expected from a singlet carbene. Whereas the assumption of spin specific reactions of carbenes is correct, the spin state itself can be changed by solvent interactions, and therefore widely accepted conclusions drawn from earlier experiments have to be revisited.