The emergence of phosphorene has generated significant interest in 2D group VA nanomaterials. Among this group, bismuthene exhibits layer-dependent direct bandgaps, high carrier mobility, and topological insulator properties because of its unique structure and ultrathin nature, distinguishing it as a promising candidate for photonic applications. Particularly, its outstanding stability in air makes bismuthene more advantageous than phosphorene for practical applications. Here, we provide a comprehensive review of recent advances regarding 2D bismuth by focusing on the aspects of methods of synthesis and photonic applications. First, the structure and fundamental properties of bismuthene are described, referring to its crystallinity and band structures, as well as to its nonlinear optical properties. Subsequently, the common synthesis methods for 2D bismuth are summarized, including both top-down and bottom-up approaches. Then, potential photonic applications based on 2D bismuth, involving nonlinear photonic devices, photocatalyst, and photodetectors, are illustrated. The performance, mechanisms, and features of the devices are discussed. Finally, the review is summarized and some challenges and future outlooks in this field are addressed.