Polyester is widely used in household products because of its good mechanical properties and wears resistance, but polyester is easy to ignite and inclined to produce droplet, so its application range is limited. The cross‐linkable magnesium hydroxide nanoparticles were incorporated into flame‐retardant polyester, which enables the phosphorus‐containing copolyester with thermal cross‐linking and anti‐meltdrop properties. The nanoparticles were achieved by in situ polymerization and acted as a nucleating agent for improving the crystalline properties of the copolyester. Furthermore, the nanoparticles also enhanced anti‐meltdrop properties and reduced the heat and gas release during the combustion process of the copolyester. The maximum heat release rate and total smoke release reduced by 39.8% and 74.4% compared with pure polyester. Specifically, the combustion products of the nanoparticles and phosphorus flame retardant could act a barrier role by covering the carbon layer to isolate air and heat, thereby resulting in excellent anti‐meltdrop properties. The simple modification method reported here realizes the collaborative modification of flame retardant and anti‐meltdrop properties of phosphorous flame‐retardant copolyesters by thermal cross‐linking.