This study unravels the changes in the water co-ordination with alkaline electrolyte concentration, and the effect of such changes in electrochemical hydrogen generation process. Water structure becomes more tetrahedrally coordinated as the alkalinity increased from 0.1M to 6 M, irrespective of the counter cations (Na + /K + /Rb + ). First principle DFT calculations also show the increase in the activation energy for water dissociation (Volmer step) as the water coordination tends more tetrahedral. We have employed ex situ and in situ