It is a challenge to develop advanced elastomers with a combination of high strength, stiffness and toughness by a relatively convenient and environmentally friendly approach. Herein, we reported a facile and environmentally friendly method to prepare hybrid crosslinked nitrile butadiene rubber (NBR) comprised of covalent and ionic bonds, and this hybrid crosslinked rubber possesses comprehensively improved mechanical properties, higher crosslinking density, deformation recovery and shape memory ability. The hybrid crosslinked NBR was prepared by incorporating 2-acrylamido-2-methyl propane sulfonic acid (AMPS) and zinc oxide (ZnO) into NBR via internal milling together with dicumyl peroxide (DCP), and then vulcanization, which is a very simple and environmentally friendly method without extra procedure or treatment. The hybrid crosslinked network in NBR has randomly distributed covalent and ionic bond crosslinks, the strong covalent bonds serve as permanent crosslinks, imparting the elasticity, whereas the weak ionic bonds reversibly rupture and reform, dissipating the energy. Because of the restricting effect of ionic bonds on segmental movement, the hybrid crosslinked NBR shows higher glass transition temperature, lower loss factor peak value and longer relaxation time. By tuning the ionic bond strength via temperature, a much smaller range of linear viscoelastic region is observed for hybrid crosslinked NBR with high content of AMPS and ZnO at a relatively higher temperature, which endows the sample with shape memory ability. This design principle of incorporating ionic bonds to strengthen vulcanized NBR should be applicable to other diene rubber materials.