First-principles calculations are performed to investigate the interaction of physisorbed small molecules, including CO, H 2 , H 2 O, NH 3 , NO, NO 2 , and O 2 , with phosphorene, and their energetics, charge transfer, and magnetic moment are evaluated on the basis of dispersion corrected density functional theory. Our calculations reveal that CO, H 2 , H 2 O and NH 3 molecules act as a weak donor, whereas O 2 and NO 2 act as a strong acceptor. While NO molecule donates electrons to graphene, it receives electrons from phosphorene. Among all the investigated molecules, NO 2 has the strongest interaction through hybridizing its frontier orbitals with the 3p orbital of phosphorene. The nontrivial and distinct charge transfer occurring between phosphorene and these physisorbed molecules not only renders phosphorene promising for application as a gas sensor, but also provides an effective route to modulating the polarity and density of carriers in phosphorene. In addition, the binding energy of H 2 on phosphorene is found to be 0.13 eV/H 2 , indicating that phosphorene is suitable for both stable room-temperature hydrogen storage and its subsequent facile release.