A new method is given to increase doping concentration of p-type ZnSe up to 1× 10i8 cm-3 through adding a little Te. This method gets over the difficulty of the high doping concentration of p-type ZnSe for many years. The external quantum efficiency (QE) of ZnSe p-n junction solar cell has been measured, and ZnSe is a good material of the top cell in the tandem solar cells. The solar cells made from ZnSe/GaAs/Ge can cover 94% of the total solar spectrum under AM (air mass) 1.5, and their theoretical efficiency is 56%.