A macroazoinitiator (MAI) containing a poly(ethylene glycol) (PEG) segment was intercalated in the gallery of sodium montmorillonite (Na-MMT). Acrylic monomers were polymerized using this MAI intercalated in Na-MMT to prepare the acrylic copolymer nanocomposite (AN), which is a multiblock copolymer composed of two segments, an acrylic copolymer and PEG intercalated in Na-MMT (Na-MMT/PEG). When AN was used to modify the reactive hot melt polyurethane adhesive (RHA), the acrylic copolymer segment and Na-MMT/PEG synergistically enhanced the initial bond strength evolution and reduced the set time, even when the amount of Na-MMT in RHA was < 1 wt%. The viscosity of RHA increased and the tensile properties of the cured RHA film decreased due to modification with AN. These variations were more evident as the Na-MMT content in AN was increased.