The configuration effect of PMAA on the formation of interpolymer complex with PLP derivatives has been studied. From the results of several experiments(e.g., turbidimetry, viscometry, polarimetry, scanning electron microscopy, and FTIR study) it is proved that the configurational sequence of PMAA affect on the formation of interpolymer complex. In thr formation of interpolymer complex with PLP, syn-PMAA shows better ability than at-PMAA in water/dioxane solvent system. We obtained the same result from the POAHP:PMAA mixtures. Because it is reported that at-PMAA make interpolymer complex with PLP through hydrogen bonding in water solvent, the great difference of behavior between syn-PMAA and at-PMAA in this study using water/dioxane (1/1) gives some probability of stereocomplex formation of syn-PMAA. Syn-PMAA has an alternative configuration of repeating units wheareas at-PMAA has irregular one. On the other hand PLP and POAHP has helical struture due to the steric restriction about the N-C bond of pyrrolidine ring without intramolecular hydrogen bond. For the formation of stereocomplex the stereo regularity is very important. In this study we worked in the water/dioxane(1/1) solvent system rater than water for the difference of solubility between PLP and POAHP. Therefore the contribution on the stabilization of complex due to hydrophobic effect reduced than in water solvent so that the configuration effect of PMAA appeared important.