The effects of stereoregularity, temperature, and solvent on the specific recognition of syndiotactic (st)-poly(methacrylic acid) (PMAA) in macromolecularly porous isotactic (it)-poly(methyl methacrylate) films were investigated to give important insights into the regularity and stability of nanospaces in the it-PMMA films as well as template polymerization. The porous it-PMMA films were fabricated on quartz crystal microbalance (QCM) substrates via the layer-by-layer (LbL) assembly of it-PMMA/st-PMAA, plus the st-PMAA extraction from the assembly. QCM analysis and infrared spectroscopy revealed the first case of stereocomplex formation using st-PMAA with lower stereoregularity (rr = 73%) in the LbL films, while st-PMAA obtained with conventional free radical polymerization (rr = 62%) was barely incorporated into the porous it-PMMA films. The maximum st-PMAA incorporation increased from 25 to 40 C, but there were almost no difference between 40 and 55 C, indicating that the it-PMMA crystallization would also be accelerated with increasing temperature. The studies on st-PMAA incorporation with various complexing solvents revealed that the host it-PMMA in the porous films could only form the original stereocomplex with 2/1 unit-molar stoichiometry (st-PMAA/it-PMMA) in acetonitrile/water or ethanol/water. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3651-3657, 2010