In this paper, TEP/PMMA composites system and SAN/TEP/PMMA composites system were prepared by in situ polymerization using methyl methacrylate (MMA), triethyl phosphate (TEP) and styrene acrylonitrile copolymer (SAN) as raw materials. The results show that TEP can improve the flame retardant performance of PMMA, and the oxygen index increases from 18.35% to 23.75%, when the content of TEP reaches 20 wt%, UL-94 reaches the V-0 level, but its thermal and mechanical properties are affected by ester group in TEP, which decreases significantly with the increase of TEP content; the mechanical and thermal properties of the composites system are improved with the increase of SAN content and tensile strength. The tensile strength increased from 37.06 MPa to 45.5 MPa, the bending strength increased from 44.58 MPa to 55.01 MPa, and the shore hardness increased from 80HD to 82HD. SAN/TEP/PMMA composites system can improve the initial decomposition temperature and increase 16 °C, the flame retardant performance of SAN/TEP/PMMA composites system is not affected by SAN content, and the visible light transmittance of both TEP/PMMA and SAN/TEP/PMMA composites system can reach 88%. This research will be of great significance in many fields such as architecture, automobile, home decoration, advertising and so on.