Taking various combinations of M = (Mo, W) and X = (C, S, Se) as examples, we propose that MX (M = transition metals, X = IV,V or VI elements) family can establish an excellent platform for both conventional and topological spintronics applications based on anisotropic Rashba-like and non-magnetic Zeeman-type spin splittings with electrically tunable nature. In particular, we observe sizeable Zeeman-like and Rashba-like spin splittings with an anisotropic nature. Meanwhile, they exhibit Rashba-like and topologically robust helical edge states when grown in ferroelectric and paraelectric phases, respectively. These MX monolayers are realized to be valley Hall insulators due to valley contrasting Berry curvatures. The carriers in these MX monolayers can be selectively excited from opposite valleys depending on the polarity of circularly polarized light. Most promisingly, the Berry curvature peaks at the two valleys can be inverted by switching the polarization direction from +P to −P , enabling the MX family to be efficient for applications based on the valley spin valve effect. The amplitude of the spin splitting can be further tuned by applying external means such as strain, electric field or polarization direction. Furthermore, considering graphene/WC as a prototype example via interfacial engineering, we show that these MX monolayers can boost the relativistic effect by coupling with the systems exhibiting extremely weak spin-orbit coupling. Depending on the polarization state, graphene/WC junction passes through the transformation from the semiconducting junction to the Shotcky barrier-free contact. Finally, we reveal that these MX monolayers could also be grown on the substrates such as WS2(001) and GaTe (001) with type-II band alignment, where electron and hole become layer splitting across the interface. Our analysis should be fairly applied to other systems with same geometry, such as WN, TaN, ZrTe, MoP, MoN, NbN, and NbS.