The aryl substituents as well as backbones in the α-diimine catalysts have a significant influence on the olefin (co)polymerization. In this work, the effect of the cycloalkyl and dibenzhydryl substituents as well as backbones of the α-diimine Pd(II) catalysts on the propylene polymerization and copolymerization has been explored. The Pd(II) catalysts led to the moderate activities (level of 104 g mol−1 h−1), tunable molecular weights (5.6–125.2 kg/mol) and highly branched (155–249/1000C) polypropylene during homopolymerization. Among the catalysts, the catalyst Pd3 with the cyclopentyl substituents and dimethyl backbone resulted in the highest molecular weight and activity in the propylene polymerization. Moreover, during the copolymerization of polypropylene-MA, the Pd(II) catalysts showed low activities and yielded low to moderate molecular weight (Mn up to 39.8 kg/mol) polar functionalized copolymers with high branching density (134–217/1000C) and tunable incorporation ratios (1.0–11.5 mol%). Overall, the catalyst Pd3 was also observed to be optimal for the copolymerization reaction, owing to the excellent copolymerization ability of propylene with MA and some other acrylic derived monomers. Further, the rigid substituents with a high steric hindrance played an unfavorable role during the (co)polymerization, which was contrary to the ethylene polymerization. In summary, compared with the rigid bulky dibenzhydryl substituents, the cyclopentyl substituents not only endowed the propylene homopolymerization system with the highest molecular weight and activity, but also provided the copolymerization system with the highest activity, incorporation ratio, and molecular weight. In addition, the incorporation of polar functionalized units could notably change the surface properties of the polypropylene materials in this work.