This work is investigating electrocatalytic performance of boron (B) in two diverse classes of graphene hybrid materials; i) the pillared graphene organic framework (GOF) which is a type of adsorbate-induced boron doped graphene and ii) the substitutionally boron doped graphene (i.e. integrated boron in disrupted graphene lattice (BG)). Raman spectroscopy and X-ray Photoelectron Spectroscopy (XPS) are among the key tools to identify chemical states of doped boron as well as its surface composition. Electron transfer efficiency of the easily synthesised GOFs (with CBO2 active chemistries) is compared with commonly cited BGs (with distinctive CBO2/BC3 moieties) which are synthesised under more rigorous thermal conditions. The intriguing feature of swelled GOFs is due to their mild solvothermal synthesising condition while managing electrochemical oxygen reduction reaction (ORR) through a dominant 4e(-) pathway (i.e. based on Rotating-Disk Electrode (RDE) results). GOF has feasibility for scalable production and a performance which is comparable to former BGs materials. The new GOF undergoes subsequent structural modifications via electrochemical polishing (i.e. chronoamperometry) to enhance its ORR efficiency and conductivity. Results indicate about a 30% boost in O-2-reduction performance of electrochemically reduced GOF (E.r.GOF) compared to native graphene organic framework and also substantial improvement in its former onset-potential (approx. 100 mV). (C) 2018 Elsevier B.V. All rights reserved.