In order to improve the accuracy and engineering feasibility of four-Satellite localization system, the frequency difference measurement is introduced to the four-Satellite TDOA (Time Difference of Arrival) localization algorithm. The TDOA/FDOA (Frequency Difference of Arrival) localization algorithm is used to optimize the GDOP (geometric dilution of precision) of four-Satellite localization. The simulation results show that the absolute position measurement accuracy has little influence on TDOA/FDOA localization accuracy as compared with TDOA localization. Under the same conditions, TDOA/FDOA localization has better accuracy and its GDOP shows more uniform distribution in diamond configuration case. The localization accuracy of four-Satellite TDOA/FDOA is better than the localization accuracy of four-Satellite TDOA.