The postpolymerization of vinyl acetate (VAc)-containing latexes with tert-butyl hydroperoxide (TBH)/ascorbic acid (ASA) as a redox initiation system was investigated. Volatile organic compounds (VOCs) such as acetone and tert-butyl alcohol were produced in this process. The influence of the TBH/AsA ratio, initiator concentration, reaction temperature, and feeding time on the reduction of residual VAc and VOC formation during the postpolymerization was investigated. A total reduction of residual VAc monomer was achieved, with the formation of VOCs kept within acceptable limits.