Vertically aligned few layered graphene (FLGs) nanoflakes were synthesized by microwave plasma deposition for various time durations ranging from 30 to 600 s to yield graphene films of varying morphology, microstructure and areal/edge density. Their intrinsic electrochemical properties were explored using Fe(CN)6 3−/4− and Ru(NH3)6 3+/2+ redox species. All the FLG electrodes demonstrate fast electron transfer kinetics with near ideal ΔEp values of 60–65 mV. Using a relationship between electron transfer rate and edge plane density, an estimation of the edge plane density was carried out which revealed a moderation of edge plane density with increase in growth time. The pristine FLGs also possess excellent electrocatalytic activity towards oxygen reduction reaction (ORR) in alkaline solutions. This ORR activity can be further enhanced by exposing the pristine FLGs to nitrogen electron cyclotron resonance plasma. The metal free N-doped FLGs exhibit much higher electrocatalytic activity towards ORR than pristine FLGs with higher durability and selectivity than Pt-based catalysts. The excellent electrochemical performance of N-doped FLGs is explained in terms of enhanced edge plane exposure, high content of pyridinic nitrogen and an increase in the electronic density of states.