The synthesis of the novel biaryl compound, 4-(2-thienyl)-1H-pyrrole-2-carbaldehyde (1), by Suzuki-Miyaura coupling conditions is reported. Compound (1) was subsequently used as a combinatorial template in the parallel solution-phase synthesis of an amine and imine compound library. The amine library was produced using reductive amination conditions, and purification was achieved by a liquid-liquid partition followed by silica chromatography to afford ten amine analogues. The imine library consisted of five compounds, which were synthesized using volatile primary amines that allowed purification by evaporation. The synthesis of the novel and related biaryl carbaldehyde, tert-butyl-2-(5-formyl-1H-pyrrol-3-yl)-1H-pyrrole-1-carboxylate (2) is also reported.