A novel macromolecular intumescent flame retardant (MIFR) was synthesized. Unsaturated polyester (UP) filled with MIFR as flame‐retardant additive was prepared. The effects of MIFR on properties such as tensile strength, impact strength, flame‐retardant behavior, thermal stability, and morphology of char were studied. Its flammability and burning behavior were characterized by UL 94 and limiting oxygen index. Twenty‐four percent of MIFR were doped into UP to get 30.5% of limiting oxygen index and UL 94 V‐0, whereas its tensile strength and the impact strength were decreased by only 7.2% and 7.0%, respectively. Activation energy for the decomposition of samples was obtained by using the Kissinger equation. The results for UP containing MIFR, compared with UP, show that the weight loss, thermal stability, and the decomposition activation energy decreased, and the char yield increased, showing that MIFR can catalyze decomposition and carbonization of UP to form an effective charring layer to protect the underlying substrate. J. VINYL ADDIT. TECHNOL., 22:350–355, 2016. © 2014 Society of Plastics Engineers