In this work, the synthesis, spectral characterization, DFT calculations, and catalytic activity of thenew Pt(II) complexes with the ligand derived from benzimidazole derivatives have been described.The new heterocyclic ligands were obtained from the reaction of o-amino-ketones with hydrazinehydrate in high yieldandPt(II) complexes prepared from the coordination of the new ligands toPt(II) cation. The new compounds have been characterized by spectral and microanalytical data.The DFT calculations at the B3LYP/6-311+G(d,p) level were also applied to gain further insightinto the geometry of Pt(II) complexes. The catalytic activity of Pt(II) complexes in Biginellireactionwas also examined as heterogeneous catalysts. The results showed that the 3,4-dihydropyrimidin-2(1H)-ones have been synthesized, in excellent yields, under solvent-free conditions, by reaction oftert-butyl acetoacetate, alcohol, arylaldehydes, and urea in the presence of Pt(II) complexes as anefficient and heterogeneous and catalyst. Manuscript profile