Poly(ethylene terephthalate) (PET) chips were coated by trisilanolphenyl–polyhedral oligomeric silsesquioxane (T‐POSS) and hexakis (para‐allyloxyphenoxy) cyclotriphosphazene (PACP) using the predispersed solution method, and PET/PACP/T‐POSS hybrids were further prepared by the melt‐blending method. The influence of T‐POSS on the rheological, thermal, and mechanical properties and flame retardancy of PET/PACP composites were discussed. The results suggest that T‐POSS was homogeneously dispersed in the PET matrix, which reduced the negative effects on polymer rheology and mechanical properties. For the PET/4%PACP/1%T‐POSS sample, the tensile strength at break and Tg increased from 29.67 MPa and 81.7 °C (PET/5%PACP) to 34.8 MPa and 85.8 °C, respectively, but the sample also self‐extinguished within 2 s, and the heat release capacity was reduced by 27.9% in comparison with that of neat PET.© 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45912.