Common commercial epoxy resin diglycidyl ether of bisphenol A or DGEBA was modified by liquid Thiokol with various ratio under different reaction conditions. A series of epoxy-thiokol copolymers were synthesized and applied as main binder in formulation of VOCs free or solvent free anti-corrosion coatings. The effect of resins, curing agent, adhesion promoter, diluents, pigments, fillers, additives, rust inhibitors, anti-rust penetrant were investigated in this work. The adhesive strength, flexibility, 720 hours neutral salt spray, water immersion test were carried out, the result showed this new VOCs free anti-corrosion coating exhibited good adhesion, flexibility, water resistance, and anti-corrosion property, even on not well prepared steel surface. This environmental-friendly anti-corrosion coatings will have prospective application in maritime industry.