A range of porous carbon‐based monolithic (PCM) rods with flow‐through pore sizes of 1, 2, 5 and 10 μm, were produced using a silica particle template method. The rods were characterised using SEM and energy‐dispersive X‐ray spectroscopy, BET surface area and porous structure analysis, dilatometry and thermal gravimetry. SEM evaluation of the carbon monolithic structures revealed an interconnected rigid bimodal porous structure and energy‐dispersive X‐ray spectroscopy analysis verified the quantitative removal of the embedded silica beads. The specific surface areas of the 1, 2, 5 and 10 μm rods were 178, 154, 84 and 125 m2/g after pyrolysis and silica removal, respectively. Shrinkage of the monolithic rods during pyrolysis is proportional to the particle size of the silica used and ranged from 9 to 12%. Mercury porosimetry showed a narrow distribution of pore sizes, with an average of ∼700 nm for the 1 μm carbon monolith. The suitability of bare and surface oxidised PCM rods for the use as a stationary phase for reversed and normal phase LC was explored. The additional modification of PCM rods with gold micro‐particles followed by 6‐mercaptohexanoic acid was performed and ion‐exchange properties were evaluated.