AbstractMorphology, stress–strain properties, and grafting have been investigated in highly phase‐separated polyurethane (PU)‐poly(n‐butyl methacrylate) (PBMA) mixtures as a function of the sequence of formation of the components, both linear (l) and crosslinked (x), in the presence of each other. In the range of 0.3–0.7 weight fraction of PU, a morphology of PBMA particles in a PU matrix results. Particle size depends on matrix viscosity at the time of PBMA formation, decreasing as viscosity increases. The PBMA (l) particles are spherical; PBMA (x) particles are irregular in shape when formed in a fluid medium but tend to become spherical as the delay time before the onset of their formation is increased. Grafting, decreasing with increasing delay time, is observed between PBMA (l) particles and the PU (x) or PU (l) matrix. The grafting results from transesterification between BMA and the polyol precursors to the PU. Two families of mechanical properties are found, depending generally more on particle shape than size. Systematic trends of property values through a series of samples of constant composition, but increasing delay times, are observed with greater variation in the series with PBMA (x) particles; the trends are explainable in terms of matrix immobilization by the particles.