Phosphorene, a two-dimensional material that can be exfoliated from black phosphorus, exhibits remarkable mechanical, thermal, electronic, and optical properties. In this work, we demonstrate that the unique structure of pristine phosphorene endows this material with exceptional quantum-mechanical performance by using first-principles calculations. Upon charge injection, the maximum actuation stress is 7.0 GPa, corresponding to the maximum actuation strain as high as 36.6% that is over seven times larger than that of graphene (4.7%) and comparable with natural muscle (20-40%). Meanwhile, the maximum volumetric work density of phosphorene (207.7 J/cm 3 ) is about three orders of magnitude larger than natural muscle (0.008-0.04 J/cm 3 ) and approximately six times larger than graphene (35.3 J/cm 3 ). The underlying mechanism of this exceptional electromechanical performance in phosphorene is well revealed from the analysis of atomic structure and electronic structure. Finally, the influence of charge on the mechanical behaviors of phosphorene is examined by mechanical tests, indicating the sufficient structural integrity of phosphorene under the combined electromechanical loading. These findings shed light on phosphorene for promising applications in developing nanoelectromechanical actuators.npj Computational Materials (2020) 6:27 ; https://doi.