Phosphorene, the single- or few-layer form of black phosphorus, was recently discovered as a two-dimensional (2D) layered material holding great promise for applications in electronics and optoelectronics. Reliable production of atomically thin, layered phosphorene with uniform size and property is essential to translate their superior properties into high-performance device applications. In this chapter, we will first introduce the fabrication of bulk black phosphorus, and then mainly summarize current methods for exfoliating phosphorene from bulk black phosphorus, specifically mechanical exfoliation and solution-phase exfoliation. The preparation of black phosphorus quantum dots and other structured layered black phosphorus is also covered to extend the forms of phosphorene. After overviewing the challenges in exfoliation of phosphorene, the possible opportunities and invaluable perspectives are discussed on production of stable and functionalized phosphorene. 2