The workfunction is an important parameter that governs several electronic phenomena occurring at the surfaces and interfaces of materials. Here, we study MXenes, which are two dimensional metal carbides and nitrides. The workfunction is strongly dependent on the terminating functional groups which induce surface dipoles and Fermi level shifts. Here, we establish a correlation between the workfunction and the adsorbate's 2p band centres. Focusing on the OH terminated MXenes which have intrinsically low workfunctions, we show that a rigid relation between the 2p band centres and workfunctions exists which resembles a volcano plot. This imposes a limit on the lowest possible workfunctions of ∼1.2 eV and sets an optimum value of the 2p band centres at which this low workfunction can occur which we determined to be ∼-5.45 eV relative to the Fermi level. We demonstrate that neither strain modulation nor doping can achieve workfunctions lower than this.