Accelerated solvent extraction (ASE) is applied for the extraction of monomers and oligomers from polymeric samples. Two polymers, nylon-6 and poly(1,4-butylene terephthalate), are selected as the model samples. The kinetics of mass transfer in ASE of polymeric samples are discussed. The effects of various experimental parameters, such as temperature, pressure, static time, flow rate, etc., on the ASE extraction efficiency are investigated systematically. Furthermore, some general guidelines for the optimization in ASE extraction of polymeric samples are given. The extraction temperature and the type of solvent used are found to be the most important parameters affecting the ASE extraction efficiency of polymeric samples.