Understanding the influence of synthesis parameters on morphology and electrochemical properties of carbon nanostructure is necessary for the development of application-tailored materials. We report on the synthesis by plasma enhanced chemical vapor deposition, morphology and catalytic activity towards oxygen reduction reaction (ORR) of hierarchical carbon nanowalls (hCNW) at different deposition times. hCNW are an advancement of common CNW possessing an increased surface area while retaining the ideal mass transport characteristics of common CNW. The hCNW structure results from a synthesis using p-xylene as an aromatic precursor. hCNW are non-doped and metal-free with easily accessible graphitic edge sites at the top of the walls and numerous defects sites located within the porous side walls, which are ideal sites for adsorption and electron transfer. hCNW reveal a high amount of different electro-chemically active sites that dominate the material character depending on the deposition time. The hCNW exhibit excellent catalytic activity towards ORR with very high ORR onset potential of 830 mV vs RHE in 0.1 mol L-1 KOH solution and selectivity towards a two electron transfer mechanism. Thereby, the onset is higher than that of several nitrogen doped carbons and one of the highest for pure carbon electrodes. In contrast to other pure carbon materials with similar onsets, oxygen doping of hCNW before the experiments could be ruled out. As such, the results of this paper indicate the existence of inner sphere ORR on sp(2)-carbon. Additionally, the results emphasize the relevance of often overlooked material properties such as surface accessibility as well as electrical conductivity for ORR. (c) 2018 Elsevier Ltd. All rights reserved.