In this study, the effects of an Al2O3 interfacial layer (IL) on the characteristics of ferroelectric field-effect transistors (FeFETs) with Hf0.5Zr0.5O2 (HZO) gate dielectrics on Si substrates were investigated. FeFETs with HZO gate dielectrics have gained considerable attention owing to their compatibility with modern fabrication processes and scalability. However, during HZO deposition on Si substrates, an ultrathin metal silicate IL with a low dielectric constant is formed in an uncontrolled manner, leading to a significant voltage drop and the generation of interface traps during device operation. To address this issue, an ultrathin Al2O3 IL with a thickness less than 2 nm was introduced between the HZO film and Si substrate via in situ atomic layer deposition. The impact of this IL on a memory window (MW) and endurance characteristics was evaluated by comparing the devices with and without an intentional Al2O3 IL. The obtained results revealed that the Al2O3 IL effectively suppressed the interface trap generation, expanded the MW, and enhanced the transistor endurance characteristics. This described approach can be potentially used for improving the reliability of FeFETs fabricated on Si substrates.