Electrodeposition of manganese/polypyrrole (Mn/PPy) nanocomposites has been recently shown to be a technologically relevant synthesis method for the fabrication of Oxygen Reduction Reaction (ORR) electrocatalysts. In this study we have grown such composites with a potentiostatic anodic/cathodic pulse-plating procedure and characterised them by a multi-technique approach, combining a suite of in situ and ex situ spectroscopic methods with electrochemical measurements. We have thus achieved a sound degree of molecular-level understanding of the hybrid co-electrodeposition process consisting of electropolymerisation of polypyrrole with incorporation of Mn. By in situ Raman spectroscopy we followed the formation of MnOx and the polymer by monitoring the build-up and development of the relevant vibrational bands. The compositional and chemical-state distribution of the as-deposited material has …