Morphological and thermal properties of immiscible and incompatible polymer blends of commercial polyamide-6 (PA-6) and poly(methyl methacrylate) (PMMA) synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization have been studied in the presence of a compatibilizer consisting of either a random copolymer of styrene-maleic anhydride (SMA) or a diblock copolymer poly(methyl methacrylate) and polystyrene (PMMA-PS) also synthesized via RAFT polymerization. Blends of PA-6/PMMA were obtained by extrusion mixing. During melt compounding in the extruder, the functional groups of the polymer components were reacted in the presence of a compatibilizer, which changed considerably the morphology of the blend. After compatibilization, particles of PMMA in the PA-6 were smaller and better dispersed. The morphology and thermal properties of the blends were characterized using scanning electron microscopy (SEM) and differential scanning calorimetry (DCS).