Poly(ethylene oxide) electrospun nanofibers with a low concentration of embedded gold nanoparticles (AuNP) were subjected to postfabrication annealing via photothermal heating from the nanoparticles. The results, including nanofibrous mat morphology, crystallinity fraction as a function of annealing time and modality, and average crystallite size, were compared with that for conventional heating at the same average temperature. Maximum crystallinity is achieved more quickly under photothermal heating, and higher maximum crystallinity values, approaching the theoretical maxima for an entangled polymer (∼80%), are obtained. Photothermal heating better preserves the unique nanostructured morphology of the nanofibrous mat whereas significant fiber thickening and loss of porosity occur under conventional annealing treatment. With photothermal heating, heat may be predominantly applied within amorphous material within the fiber, which provides energy for the amorphous chains to reorient and then possibly crystallize but while preserving existing crystalline regions as well as the temperature-fragile nanofiber surface. This occurs because nanoparticles are spontaneously segregated within amorphous material due to their characteristic size. In the complex environment of a polymeric nanofiber where crystalline, aligned amorphous, and random amorphous material are all present, further spontaneous segregation of the AuNP to the random amorphous material may occur which enables targeting of this higher barrier to crystallization population, leading to very high final crystallinity fractions.