Alternating‐rich copolymer of vinylboronic acid pinacol ester (VBpin) and maleic anhydride (MAH) was found to catalyze direct dehydrative esterification of carboxylic acid and alcohol. The key to the catalytic function is the activation of the MAH unit by the neighboring Lewis acidic boron directly connected to the backbone through the formation of five‐membered ring. The effects of the side‐chain cooperation were clarified through comparisons with the polymers having similar structures and a conventional titanium catalyst as well as the analyses of reactions with carboxylic acid or alcohol. The catalytic activity was enhanced as the molecular weight was higher, which is owing to the structural feature that boron is directly attached to the backbone. The cooperative catalysis is of interest because of its conceptual similarity with enzyme.