Acrylate polymers are a leading class of polymers that offer easy synthesis and structural versatility. Polyacrylates were mostly synthesized by polymerizing various acrylate monomers; postpolymerization modification (PPM) has now emerged as a useful alternative. The PPM route offers improved synthetic efficiency and can be used to produce synthetically challenging structures. This review categorizes PPM examples by the types of reactions, from classical esterification of carboxylic acid to catalytic transesterification of esters. The pros and cons of various approaches are discussed, and remaining challenges are examined.