The first access to N-1, N-4 disubstituted pyrrolo[2,3-d][1,2,3]triazoles is reported. The series were generated using a “one-pot” MCR, leading to a single regioisomer of the attempted heteroaromatic skeleton in good yields. Next, the functionalization of C-5 and C-6 positions was investigated. (Het)aryl groups were introduced at the C-5 and C-6 positions of the pyrrolo[2,3-d][1,2,3]triazoles using regioselective electrophilic brominations followed by Suzuki–Miyaura cross coupling reactions. Palladium-catalyzed cross-coupling conditions were optimized and a representative library of various boronic acids was employed to establish the scope and limitations of the method.