We developed ReaxFF parameters for phosphorus and hydrogen to give a good description of the chemical and mechanical properties of pristine and defected black phosphorene. ReaxFF for P/H is transferable to a wide range of phosphorus- and hydrogen-containing systems including bulk black phosphorus, blue phosphorene, edge-hydrogenated phosphorene, phosphorus clusters, and phosphorus hydride molecules. The potential parameters were obtained by conducting global optimization with respect to a set of reference data generated by extensive ab initio calculations. We extended ReaxFF by adding a 60° correction term, which significantly improved the description of phosphorus clusters. Emphasis was placed on the mechanical response of black phosphorene with different types of defects. Compared to the nonreactive SW potential (Jiang, J.-W. Nanotechnology 2015, 26, 315706), ReaxFF for P/H systems provides a significant improvement in describing the mechanical properties of the pristine and defected black phosphorene, as well as the thermal stability of phosphorene nanotubes. A counterintuitive phenomenon is observed that single vacancies weaken the black phosphorene more than double vacancies with higher formation energy. Our results also showed that the mechanical response of black phosphorene is more sensitive to defects in the zigzag direction than that in the armchair direction. In addition, we developed a preliminary set of ReaxFF parameters for P/H/O/C to demonstrate that the ReaxFF parameters developed in this work could be generalized to oxidized phosphorene and P-containing 2D van der Waals heterostructures. That is, the proposed ReaxFF parameters for P/H systems establish a solid foundation for modeling of a wide range of P-containing materials. © 2017 American Chemical Society.