This paper reports on the control of the direct-contact La-silicate/Si interface structure with the aim of achieving scaled equivalent oxide thickness (EOT) and small interface state density. The interface state density at the direct-contact La-silicate/Si interface is found to be reduced to <formula formulatype="inline" xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"><tex Notation="TeX">$\hbox{1.6} \times \hbox{10}^{11}\ \hbox{cm}^{-2}\hbox{eV}^{-1}$</tex></formula> by annealing at 800 <formula formulatype="inline" xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"><tex Notation="TeX">$^{\circ}\hbox{C}$</tex></formula> for 30 min in forming gas ambient, whereas excess silicate reaction concurrently induced a significant increase in EOT. By utilizing metal-inserted poly-Si (MIPS) stacks and their annealing at high temperature, the increase in EOT is drastically suppressed. At the same time, a superior interfacial property is obtained because the Si layer in the MIPS stacks prevents the excess oxygen diffusion from the atmosphere during the annealing process. As a result, the effective electron mobility of 155 <formula formulatype="inline" xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"><tex Notation="TeX">$\hbox{cm}^{2}/\hbox{V}\cdot{s}$</tex></formula> at 1 MV/cm and an EOT of 0.62 nm are successfully achieved by utilizing direct-contact La-silicate/Si structure. This result is comparable with the recorded effective electron mobility achieved by utilizing Hf-based oxides/Si structure. This demonstrates the advantage of our proposed method to realize the scaled EOT with a superior interfacial property for state-of-the-art metal–oxide–semiconductor field-effect transistors.