A novel high-efficient flame retardant epoxy grafted poly-acrylic resin modified by phosphorus and nitrogen was successfully synthesized by radical grafting polymerization and solution polymerization simultaneously. The flame retardancy of copolymer resin was investigated using thermogravimetric analysis (TGA), cone calorimetric test (CONE), limiting oxygen index (LOI) and so on. The micro-morphology and chemical composition of char formed after a CONE calorimetric test was analyzed using scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS), respectively. The Kissinger method was used to evaluate the kinetics of thermal decomposition on copolymer resin. The results showed that the flame retardant property of copolymer resin increased with the increase in phosphorus content. With the increase in nitrogen content, however, the flame retardant property first increased and then decreased. The flame retardant property of the resin was the best and the limiting oxygen index could reach 34.3% when the phosphorus content and nitrogen content of the copolymer resin were 6.45 wt% and 2.33 wt%, respectively. Meanwhile, nitrogen-containing compounds will interact with phosphorus-containing compounds to form P-N intermediates during combustion, which have stronger dehydration and carbonization and could further enhance the flame retardant performance of the resin and generate phosphorus-nitrogen synergistic interactions.