Phosphate tailings (PTs) are solid waste, which is produced by phosphate flotation. In this work, PTs were used as raw materials for the preparation of diethylenetriamine pentamethronic acid (DTPMP) intercalated trimetal (Ca-Mg-Al) layered double hydroxides (TM-DTPMP LDHs) by co-precipitation method. TM-DTPMP LDHs were characterized by X-ray diffraction, fourier-transform infrared spectroscopy, scanning electron microscopy, differential thermal gravimetric analysis, X-ray photoelectron spectroscopy and applied as a flame retardant to improve the fire safety of epoxy resin (EP). The results showed that the composite materials exhibited obvious layered structure. After intercalation, layer spacing increased from 0.783 to 1.78 Å. When the amount of TM-DTPMP LDH in EP was 8%, the limitted oxygen index of the composite material increased from the original 19.2% to 30.2%. In addition, Cone calorimeter (CC) and Raman spectrum results indicated that with the addition of TM-DTPMP LDHs, the value of heat release rate peak (pHRR) and total heat release (THR) were reduced by more than 43% and 60%, while the value of smoke formation rate (pSPR) and the total smoke production (TSP) decreased nearly 64% and 83%, respectively. The significant reduction in the release of combustion heat and harmful smoke during EP combustion may be attributed to the synergistic flame-retardant effect between hydrotalcite and DTPMP. This work exhibited great potential for the green recycling of PTs and the enhancement of the fire safety of EP.