Without extra heating, Al2O3 thin films were deposited on a hydrogen-terminated Si substrate etched in hydrofluoric acid by using a self-built electron cyclotron resonance (ECR) plasma-assisted atomic layer deposition (ALD) device with Al(CH3)3 (trimethylaluminum; TMA) and O2 used as precursor and oxidant, respectively. During the deposition process, Ar was introduced as a carrier and purging gas. The chemical composition and microstructure of the as-deposited Al2O3 films were characterized by using X-ray diffraction (XRD), an X-ray photoelectric spectroscope (XPS), a scanning electron microscope (SEM), an atomic force microscope (AFM) and a high-resolution transmission electron microscope (HRTEM). It achieved a growth rate of 0.24 nm/cycle, which is much higher than that deposited by thermal ALD. It was found that the smooth surface thin film was amorphous alumina, and an interfacial layer formed with a thickness of ca. 2 nm was observed between the Al2O3 film and substrate Si by HRTEM. We conclude that ECR plasma-assisted ALD can grow Al2O3 films with an excellent quality at a high growth rate at ambient temperature. Without extra heating, Al2O3 thin films were deposited on a hydrogen-terminated Si substrate etched in hydrofluoric acid by using a self-built electron cyclotron resonance (ECR) plasma-assisted atomic layer deposition (ALD) device with Al (CH3) 3 ; TMA) and O2 used as precursor and oxidant, respectively. During the deposition process, Ar was introduced as a carrier and purging gas. The chemical composition and microstructure of the as-deposited Al2O3 films were characterized by using X-ray diffraction ), an X-ray scanning spectrometer (XPS), an atomic force microscope (AFM) and a high-resolution transmission electron microscope (HRTEM). It achieved a growth rate of 0.24 nm / cycle, which was much higher than that deposited by thermal ALD. It was found that the smooth surface thin film was amorphous alumina, and an interfacial layer formed with a thickness of ca. 2 nm was observed between the Al2O3 film and substrate Si by HRTE M. We conclude that ECR plasma-assisted ALD can grow Al2O3 films with an excellent quality at a high growth rate at ambient temperature.