The adhesion behavior of semi-interpenetrating polymer networks (semi-IPNs) of linear polystyrene (PS) in crosslinked poly-2-ethylhexylmethacrylate (EHMA) was studied by variation of the bulk and surface morphology, i.e., domain size, continuity, and concentration in the domains. Semi-IPNs were prepared by liquid-liquid demixing upon cooling of a homogeneous solution of PS in methacrylate monomer, followed by gelation of the PS-rich phase and UV polymerization of the methacrylate resin, Welding of films allowed the preparation of larger objects provided that (1) the samples were phase separated to a high degree and contained domains with a high PS concentration (>90%) and (2) polystyrene was present at the interface. For semi-IPN films, a linear dependence of the adhesion strength on the (crack healing time)(1/4) was obtained. Based on these considerations, a process was developed to obtain melt-processable semi-IPN particles, by quenching droplets of the polymer solution into a cold liquid, These particles obtained a PS-rich skin layer and showed good adhesion after blending with a thermoplast.