Poly(vinylpyrrolidone) (PVP) nanofibers containing 2,9,16,23-tetra-tert-butyl-29H,31H- phthalocyanine free base (H2TTBPc) and fullerene (C60) were prepared by electrospinning. The nanofibers were characterized by scanning electron microscopy, UV-visible absorption spectroscopy, and photoluminescence (PL) spectroscopy. Under the various conditions of electrospinning such as the concentrations of PVP and an organic volatile salt, and the sizes of the nozzle, we could find good conditions to obtain as-spun nanofibers of which average diameter was 429nm. The incorporated H2TTBPc in the nanofibers shows highly oriented -type crystalline state in the presence of C60 as compared with that of the film prepared by a casting method.