Layer by layer (LBL) self-assembly coatings upon expandable polystyrene (EPS) surface play an important role in improving its flame retardancy. However, a large number of layers is needed to achieve a satisfied fire performance, and the coatings are difficult to adhere on the inert EPS surface, resulting in the poor durability. In this work, the surface of EPS was activated by ultraviolet ozone (UVO) with the appearance of oxygen contained groups, then a LBL coating with only two bilayers (branched polyethyleneimine (BPEI)-kaolinite (kaol)-BPEI-diethylene triamine penta (methylene phosphonic acid)) was covalently connected on the EPS surface. Compared with neat EPS, the obtained E-K5D30 sample increased the value of limiting oxygen index (LOI) from 18.8 % to 37.7 %, improved the ignition time from 59 s to 95 s, reduced the peak heat release rate (pHRR) value from 282.0 kW/m2 to 220.9 kW/m2, and enhanced the char residues from 6.3 % to 32.3 % after the combustion. Moreover, an ultraviolet (UV) curing layer with P/N elements was prepared upon E-K5D30 sample to maximize the flame retardant durability. A novel amino-intercalated kaol was used to play a smoke suppression role. The results showed that E-K*5D30-P8N3 sample further increased the LOI to 39.2 %. Even after 12 h washing, the E-K*5D30-P8N3 sample exhibited a slight LOI reduction to 37.8 %, and fire performance index (FPI) value of 0.405 m2·s/kW, showing the successful construction of coatings with good fire safety and flame retardant durability.