Reactions of ligands (E)‐N′‐(2,6‐diisopropylphenyl)‐N‐(4‐methylpyridin‐2‐yl)benzimidamide (L1), (E)‐N′‐(2,6‐diisopropylphenyl)‐N‐(6‐methylpyridin‐2‐yl)benzimidamide (L2), (E)‐N′‐(2,6‐dimethylphenyl)‐N‐(6‐methylpyridin‐2‐yl)benzimidamide (L3), (E)‐N′‐(2,6‐dimethylphenyl)‐N‐(4‐methylpyridin‐2‐yl)benzimidamide (L4), and (E)‐N‐(6‐methylpyridin‐2‐yl)‐N′‐phenylbenzimidamide (L5) with [Pd(NCMe)2Cl2] furnished the corresponding palladium(II) precatalysts (Pd1–Pd5), in good yields. Molecular structures of Pd2 and Pd3 revealed that the ligands coordinate in a N^N bidentate mode to afford square planar compounds. Activation of the palladium(II) complexes with para‐tolyl sulfonic acid (PTSA) afforded active catalysts in the methoxycarbonylation of a number of alkene. The resultant catalytic activities were controlled by the both the complex structure and alkene substrate. While aliphatic substrates favored the formation of linear esters (>70%), styrene substrate resulted in the formation of predominantly branched esters of up to 91%.