Molybdenum based compounds are an emerging class of non-metallic catalytic materials for the hydrogen evolution reaction (HER) in acidic media. However, most of them lose considerable catalytic performance and exhibit poor long-term stability in alkaline media. Here, planar molybdenum oxide, with high alkaline stability and ordered intracrystalline pores, is developed as the HER candidate. The pores with diameters in the order of ∼5-7 Å are HER-active, and appear after an NH4 + doping-driven phase transition from the orthorhombic to hexagonal phase. Such a unique structure facilitates the diffusion of ionic entities and water molecules to the HER sites and helps in the removal of gaseous products, therefore improving the surface active area and reaction kinetics. These intracrystalline pores also reduce the long term stress on electrodes. The corresponding HER activity is extremely stable for >40 h in an alkaline medium at an overpotential of 138 mV with a Tafel slope of 50 mV dec-1. Such properties offer a superior combination compared to those of other reported molybdenum based nanostructures, hence providing a great opportunity for developing high-performance alkaline non-metal HER catalysts.