The control of the stereochemistry of macromolecules is a very important goal, and coordination-insertion polymerization is superior with respect to the other polymerization methods for its achievement. In this contribution, we focus on Pd(II) homogeneous catalysts for the stereocontrolled synthesis of CO/vinyl arene polyketones. We developed a library of aldo- and keto-iminopyridine ligands N-N′ that feature an α- or β-naphthyl or anthracenyl moiety on the imino nitrogen atom (Nimm). With such ligands, the Pd(II) monocationic complexes [Pd(CH3)(CH3CN)(N-N′)][PF6] were synthesized. NMR spectroscopy shows that in solution, each complex exists as an equilibrium mixture of cis and trans stereoisomers, the latter having the CH3 ligand opposite to the Pd–Nimm bond. The isomeric population depends on the N-N′ ligand: an almost 1:1 ratio is found for the ketimine complexes, whereas those with the aldimines show a preference for the trans geometry. These complexes generate very efficient catalysts for the CO/vinyl arene copolymerization. Catalyst performances depend both on the nature of N-N′ and of the vinyl arene comonomer. The ketimine-based catalysts are more stable and more productive than the aldimine counterpart, leading to prevailingly syndiotactic macromolecules of high Mw (up to 280 kDa). The aldimine derivatives produce copolymers with isotactic and syndiotactic stereoblocks of different lengths depending on the vinyl arene. The effect of the prochiral monomer on the copolymer tacticity is steric in nature as demonstrated by the stereochemistry of the obtained CO/4-fluorostyrene polyketone, whose synthesis is reported here for the first time. As a conclusion, we have now demonstrated that when catalysts with nonsymmetric ancillary ligands are used, and stereoisomers are present, the stereochemistry of the copolymerization is driven by both the catalyst isomeric distribution and the prochiral comonomer.