A type of polycyclotriphosphazene derivative (PCTPD), hexasulfanilic acid polycyclotriphosphazene (HSACP) and HSACP grafting SPEEK, sulfonated poly[2-(petachloropolycyclotriphosphazene-oxy)] etheretherketone (SPPSACPEEK) were synthesized, which were characterized by FTIR and $^{31}P$ NMR. Then three types of composite membranes such as HSACP grafting SPEEK, HSACP blending SPEEK, and nano $Y_2O_3$ doping and HSACP grafting SPEEK, respectively, were continuously prepared by solution-casting method. Comparing to SPEEK membranes with different amount of HSACP grafted or blended, grafting 15 wt% HSACP and doping 10 wt% nano $Y_2O_3$ SPEEK membrane conducted outstanding overall behavior of proton conductivity reaching $3.18 { imes}10^{-2}$ S/cm at $90^{circ}C$ which was merely junior to SPEEK with 15 wt% HSACP grafted, methanol permeability coefficient getting $9.46{ imes}10^{-8}cm^2{cdot}s^{-1}$, swelling degree of 20.9% and solid residue of 98.98% which was superior to all specimen.