Macroporous carbon materials (MCMs) are used extensively for many electrocatalytic applications, particularly as catalysts for oxygen reduction reactions (ORRs)—for example, in fuel cells. However, complex processes are currently required for synthesis of MCMs. We present a rapid and facile synthetic approach to produce tailored MCMs efficiently via pyrolysis of sulfonated aniline oligomers (SAOs). Thermal decomposition of SAO releases SO2 gas which acts as a blowing agent to form the macroporous structures. This process was used to synthesise three specifically tailored nitrogen (N)-doped MCM catalysts: N-SAO, N-SAO (phenol formaldehyde) (PF) and N-SAO-reduced graphene oxide (rGO). Analysis using Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy (FTIR) and X-ray diffraction (XRD) analysis confirmed the formation of macropores (100–350 µm). Investigation of ORR efficacy showed that N-SAOPF performed with the highest onset potential of 0.98 V (vs. RHE) and N-SAOrGO showed the highest limiting current density of 7.89 mAcm−2. The macroporous structure and ORR efficacy of the MCM catalysts synthesised using this novel process suggest that this method can be used to streamline MCM production while enabling the formation of composite materials that can be tailored for greater efficiency in many applications.