CaZn2(PO4)2 and β-BaB2O4 nanopowders were firstly synthesized by an ultrasonic-aid chemical precipitation method. Then BaB2O4 was mixed with CaZn2(PO4)2 to prepare CaZn2(PO4)2-BaB2O4 nanopowder ecological anticorrosive pigment. The TG-DTA, XRD and TEM measurements were used to characterize the structure and morphology of products. The activation of pigment has been improved by two ways: one is the synthesis of well-dispersed nanometer-sized powder with narrow distribution; the other way is to mix the two kinds of pigment together to generate a hybrid ecological pigment. Finally, the anticorrosive experiments of the product were investigated in aqueous alkyd paints. The result of anticorrosive performance indicates that the as-obtained hybrid pigments exhibit more excellent properties than commercial zinc phosphate and ZPA from Germany.