Recently, layered two-dimensional (2D) semiconductor materials composed of group 15 elements (pnictogens) are demonstrated as efficient photocatalysts in various applications. However, only little attention is given to the investigation of their catalytic properties, and even there is no example of the photocatalytic application of bismuthene so far. Here we report for the first time on the use of 2D bismuthene as a photocatalyst in a liquidphase organic transformation. 2D bismuthene is proven to be an efficient photocatalyst that can be operated under various reaction conditions including indoor light illumination, darkness, outdoors and low temperature for the photoredox C-H arylation of (hetero)arenes with high product yields. The presented bismuthene catalyzed photoredox C-H arylation protocol works efficiently on a broad substrate scope of (hetero)arenes with aryl diazonium salts bearing electron-withdrawing and electron-donating groups. Moreover, a density functional theory (DFT) study reveals mechanistic details that lie behind the catalytic activity of bismuthene.