Although the study of black phosphorene (BP) and its isomers has attracted enormous attention, the method of synthesizing high-quality samples in a large area is still pending. Here we explore the potential of using the chemical vapor deposition method to synthesize large-area two-dimensional (2D) phosphorene films on metal surfaces. Our ab initio calculations show that BP can be synthesized by using tin (Sn) as a catalyst, while one of its isomers, blue phosphorene (BLP), is very possible to be synthesized by using most other metals, such as Ag and Au. Besides, our study also suggests that the large binding energy between the 2D phosphorene and the active metal substrate may prohibit the exfoliation of the 2D phosphorene for real applications and, therefore, tin, silver and gold are predicted to be the most suitable catalysts for the synthesis of BP and BLP.