The pyrolysis of polymethyl acrylate is reported with identification of the major pyrolysis products. The mechanism involving random homolytic scission of the chain followed by a series of intermolecular and intramolecular transfer reactions as proposed by Cameron and Kane and extended by Haken, Ho, and Houghton is further developed. Reaction mechanisms are postulated for all of the products produced and ion fragmentation mechanisms for the various spectra produced are shown. The paper also forms the basis for a study of the homologous alkyl polyacrylates, both straight and branched chain esters being considered these having not been previously extensively studied.