The invention relates to a composite phosphating solution of P-Ca-V on the surface of a magnesium alloy and a method for chemical conversion treatment. The solution is characterized in that each liter of the composite phosphating solution comprises the following compositions: 4 to 20 milliliters of 85 percent phosphoric acid of, 5 to 30 grams of sodium dihydrogen phosphate, 10 to 40 grams of calcium nitrate, 0.5 to 10 grams of benzene sulfonic acid sodium salt, 0.5 to 5 grams of ammonium metavanadate, and the balance being water. The method comprises the following steps: pre-degreasing, degreasing, secondary water washing, acid washing, secondary water washing, alkaline etching, secondary water washing, chemical transformation, secondary water washing, pure water washing, and drying. Taking an AZ91D magnesium alloy as an example, 48 hours after a corrosion resistance salt spray test after the treatment by the method of the invention, the corrosion area of the AZ91D magnesium alloy is less than 1 percent; the paint film adhesive force is at 0 level by a grid method and is obviously superior to the performance of a chromate conversion coating; and the formed chemical conversion coating does not contain crystal water. The composite phosphating solution has the synergistic reaction of Ca and V, as well as the functions of a corrosion inhibitor and a wetting agent of the benzene sulfonic acid sodium salt.