Metastable modification of MoS2 (1T) is widely recognized as a hopeful non-precious electrocatalyst in hydrogen production. This paper describes an approach to impart a superambient temperature stability to 1T-MoS2 by incorporating it in 2D hybrid architecture with cationic monomolecular phenanthrolinium (PhenH+) hydrate layers. The atomic structure and bonding interactions of the assembled architecture revealed by PXRD, TEM, XPS, Raman and UV-Vis spectroscopy data coupled with DFT calculations and quantum theory of atoms in molecules (QTAIM) analysis suggest that the 1T-MoS2 sheets are involved in strong bonding with the PhenH-H2O layers. This results in a highly stable layered system, which is kept intact in 0.5 M sulfuric acid electrolyte and tolerates superambient temperature heating. As compared with pure 1T-MoS2, the compound with a phenanthroline interlayer provides greater activity and better current-voltage efficiency in electrocatalytic hydrogen evolution after heating treatment owing to stabilization of the 1T phase. The obtained results could be useful for the design of novel electrocatalytic devices exploiting 1T-MoS2 modification.