Isotactic, atactic, and syndiotactic poly(methyl methacrylates) (PMMAs) (designated as iPMMA, aPMMA, and sPMMA) were mixed with poly(styrene-co-p-hydroxystyrene) (abbreviated as PHS) containing 15 mol % of hydroxystyrene separately in 2-butanone to make three polymer blend systems. Differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) spectroscopy were used to study the miscibility of these blends. The three polymer blends were found to be miscible, because all the prepared films were transparent and there was a single glass transition temperature (T-g) for each composition of the polymers. T-g elevation (above the additivity rule) is observed in all the three PMMA/PHS blends mainly because of hydrogen bonding. If less effective hydrogen bonding based on the FTIR evidence is assumed to infer less exothermic mixing, sPMMA may not be miscible with PHS over a broader range of conditions as iPMMA and aPMMA.