Herein, a four-coordinated organoboron compound, aminoquinoline diarylboron (AQDAB), is utilized as the photocatalyst in the oxidation of silane to silanol. This strategy effectively oxidizes Si–H bonds, affording Si–O bonds. Generally, the corresponding silanols can be obtained in moderate to good yields at room temperature under oxygen atmospheres, representing a green protocol to complement the existing preparation methods for silanols.