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Phosphorus–nitrogen dual-doped carbon nanoparticles (PN-CNPs) have been successfully synthesised using chemical vapour deposition (CVD), in the presence of triphenylphosphine and acetonitrile. PN-CNPs are used as carbon support for Pd and employed as electrocatalyst in hydrogen evolution reactions. The prepared Pd/PN-CNPs electrocatalyst was subjected to morphological and electrochemical studies carried out using FE-SEM, EDS, ICP, XRD, CV, and LSV techniques. The membrane electrode assemblies (MEAs) were prepared and tested in 25 cm2 area PEM cell setup and the test results obtained are promising as the cell voltage is 1.9 V at 1000 mA cm−2 at 80 °C. Furthermore, the cell setup was operated continuously for 500 h and has shown stable performance without any hindrance in electrochemical activity. [ABSTRACT FROM AUTHOR]