Multicomponent reactions are of utmost importance at generating a unique, wide, and complex chemical space. Herein we describe a novel multicomponent approach based on the combination of the isonitrile‐tetrazine (4+1) cycloaddition and the Ugi four‐component reaction to generate pyrazole amide derivatives. The scope of the reaction as well as mechanistic insights governing the 4H‐pyrazol‐4‐imine tautomerization are provided. This multicomponent process provides access to a new chemical space of pyrazole amide derivatives and offers a tool for peptide modification and stapling
