The determination of the standard potential of alkyl primary amines is reported for the first time using the nanosecond equilibrium method. The versatility and accuracy of the method demonstrates that it is not only an alternative to the classical and modern electrochemical methods, but also a powerful tool for quantifying inductive and/or solvation effects in a related family of compounds. Two different trends were observed depending on alkyl chain length. For "short-chain" alkyl primary amines, where the solvation around the amino group is expected to be the same, the standard potential value appears to follow a linear relationship with the number of carbon atoms, which indicates that the methylene group (-CH2-) causes an inductive effect that is responsible for the stabilization of the amine cation radical. Meanwhile, the E° rises slightly to a constant potential value 1.500 V for ̀long-chaiǹ unbranched alkyl primary amines. This interesting result can be explained by a steric inhibition of solvation around the amino group due to a fold of the long alkyl chain following a solvent exclusion mechanism. © 2007 American Chemical Society.