Herein, we reveal the temperature-dependent broadening of the Mott gap in layered α-RuCl₃, together with a distinct transition in the range of 100–130 K, through surface morphology and electronic structure characterizations using scanning tunneling microscopy and scanning tunneling spectroscopy, respectively. Furthermore, layer-dependent measurements indicate an enhanced phase transition and Kitaev interactions with decreasing thickness. These results show that low-dimensional α-RuCl₃ films differ from their bulk state owing to their unique structural and electronic properties, providing an ideal model platform for exploring Kitaev physics.