Poly[(alanino ethyl ester)(0.67) (glycino ethyl ester)033 phosphazene] (PAGP) was synthesized, and morphology and diameter of the electrospun PAGP nanofibers were systematically evaluated by using a cool field emission scanning electron microscope (SEM) with changing the important processing variables such as applied voltage, polymeric concentration, and ambient temperature. The average diameter of PAGP nanofibers was inversely proportional to the applied voltage, but increased with the increase of solution concentration. Lower environmental temperature was unfavorable due to the nanofibers conglutination.