The ability to modulate the nucleophilicity and Lewis basicity of N-heterocyclic carbenes is pivotal to their application as organocatalysts. Herein we examine the impact of the N-substituent on the nucleophilicity and Lewis basicity. Four N-substituents popular in NHC organocatalysis, namely, the N-2,6-(CH₃O)₂C₆H₃, N-Mes, N-4-CH₃OC₆H₄, and N-tert-butyl groups, have been examined and found to strongly affect the nucleophilicity. Thus, the N-2,6-(CH₃O)₂C₆H₃ group provides the most nucleophilic imidazolylidene NHC reported and the N-tert-butyl group one of the least. This difference in nucleophilicity is reflected in the catalyst efficiency, as observed with a recently reported trienyl ester rearrangement.