© 2016 Macmillan Publishers Limited. Symmetry-breaking has been known to play a key role in non-centrosymmetric superconductors with strong spin-orbit interactions (SOIs; refs,). The studies, however, have been so far mainly focused on a particular type of SOI, known as the Rashba SOI (ref.), whereby the electron spin is locked to its momentum at a right-angle, thereby leading to an in-plane helical spin texture. Here we discuss electric-field-induced superconductivity in molybdenum disulphide (MoS 2), which exhibits a fundamentally different type of intrinsic SOI, manifested by an out-of-plane Zeeman-type spin polarization of energy valleys. We find an upper critical field of approximately 52 T at 1.5 K, which indicates an enhancement of the Pauli limit by a factor of four as compared to that in centrosymmetric conventional superconductors. Using realistic tight-binding calculations, we reveal that this unusual behaviour is due to an inter-valley pairing that is symmetrically protected by Zeeman-type spin-valley locking against external magnetic fields. Our study sheds light on the interplay of inversion asymmetry with SOIs in confined geometries, and its role in superconductivity.