MBHA (4-methylbenzhydrylamine) resin has been extensively used as a solid support for the synthesis of peptide amides. Herein, we prepared the core–shell-type MBHA resin by benzotriazole-catalyzed amidoalkylation and partial hydrolysis. The core–shell structure of the MBHA resin was confirmed by two-photon microscopy and its synthetic performance in solid-phase peptide synthesis (SPPS) was evaluated.