Spin polarization of Co-based Heusler alloys with various compositions was examined by point contact Andreev reflection (PCAR) measurements for the purpose of searching half metallic Heusler alloys. It was shown that, in some 3-element Heusler alloys, an addition of the appropriate 4-th element enhances the spin polarization of conduction electrons. High magnetoresistance ratio was obtained in current-perpendicular-to-plane giant magnetoresistence (CPP-GMR) devices by using the Co_2FeAl_<0.5>Si_<0.5> Heusler alloy as ferromagnetic electrodes.