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.