In this study, Zr active species were implanted into a ZSM-5 zeolite framework to form a solid acid catalyst through steam treatment and the liquid-solid isomorphous substitution process. The as-synthesized Zr-ZSM-5-st catalyst ensured excellent esterification of trimethylolpropane and fatty acids (FAs) to achieve a polyol ester production yield of 94.41%. Combined with N₂ physisorption, X-ray diffraction, Fourier transform infrared spectroscopy, ultraviolet-visible spectroscopy, transmission electron microscopy mapping, X-ray photoelectron spectroscopy, NH₃ temperature-programmed desorption, and inductively coupled mass plasma spectroscopy were conducted. The results revealed that the excellent performance of Zr-ZSM-5-st catalyst could be attributed to the enhanced acidity and the developed surface area and pore structure.