Using the orthorhombic layered Na2FePO4F cathode material as a model system we identify the bonding of the alkali metal cations to the semilabile oxygen atoms as an important factor affecting electrochemical activity of alkali cations in polyanion structures. The semilabile oxygens, bonded to the P and alkali cations, but not included into the FeO4F2 octahedra, experience severe undercoordination upon alkali cation deintercalation, causing an energy penalty for removing the alkali cations located in the proximity of such semilabile oxygens. Desodiation of Na2FePO4F proceeds through a two-phase mechanism in the Na-ion cell with a formation of an intermediate monoclinic Na1.55FePO4F phase with coupled Na/vacancy and Fe2+/Fe3+ charge ordering at 50% state of charge. In contrast, desodiation of Na2FePO4F in the Li-ion cell demonstrates a sloping charge profile suggesting a solid solution mechanism without formation of a charge-ordered intermediate phase. A combination of a comprehensive crystallographic study and extensive DFT-based calculations demonstrates that the difference in electrochemical behavior of the alkali cation positions is largely related to the different number of the nearest neighbor semilabile oxygen atoms, influencing their desodiation potential and accessibility for the Na/Li chemical exchange, triggering coupled alkali cation-vacancy ordering and Fe2+/Fe3+ charge ordering, as well as switching between the "solid solution" and "two-phase" charging mechanistic regimes.