The miscibility and phase behavior in a binary blend of isotactic polystyrene (iPS) and poly(cyclohexyl methacrylate) (PCHMA) were investigated by differential scanning calorimetry, optical microscopy (OM), and solid-state C-13 cross-polarity/magic-angle spinning NMR. The iPS/PCHMA blend was miscible when all compositions showed a single composition-dependent glass-transition temperature (T-g) and when the blend went through a thermodynamic phase transition upon heating to above the lower critical solution temperature as determined by OM measurements. The H-1 NMR spin-relaxation times in the laboratory frame (T-1(H)) and in the rotating frame (T-1rho(H)) for iPS/PCHMA blends with various compositions and neat components were directly measured through solid-state C-13 NMR. The results of T-1(H) indicated that the blends are homogeneous, at least on a scale of 75-85 nm, confirming the miscibility of the system. The single decay and composition-dependent T-1rho(H) values for each blend further demonstrated the blends are homogeneous on a scale of 2.5-3.5 nm. The results suggested that iPS and PCHMA are intimately mixed at the molecular level within the blends at all compositions. The tacticity of polystyrene does not seem to adversely influence the miscibility in blends of iPS/PCHMA. (C) 2003 Wiley Periodicals, Inc.