We explore the electronic structure of two-dimensional (2D) MnPSe3/MoS2 van der Waals (vdW) heterostructures based on density functional theory. A novel spin splitting at the valance band maximum of MnPSe3 appears in some specific stacking models due to Mn d orbital hybridization. The simultaneous spin and valley splitting can be achieved by interfacial coupling, which is attractive for manipulation of the valley and spin degrees of freedom. More importantly, due to the antiferromagnetic ordering of manganese, the opposite spin moments at K and K' valleys can be observed by transforming configurations, which realizes the tunable spin splitting states. Our theoretical work opens up the opportunities of valley and spin related applications of MnPSe3/MoS2 vdW heterostructures and offers a practical avenue for exploring novel devices based on the spin and valley degrees of freedom.