Mesoporous-TiO 2 nanoparticles (meso-TiO 2 ) and nano-TiO 2 particles (nano-TiO 2 ) were synthesized and characterized using scanning electron microscopy. The electrochemical behaviours of carbon paste electrodes (CPE), nano-TiO 2 /CPE and meso-TiO 2 /CPE were investigated using K 3 [Fe(CN) 6 ] as the electrochemical probe. It was observed that the peak potential separation was remarkably decreased at the meso-TiO 2 /CPE with higher peak currents in comparison with the other two CPEs. Moreover, the electrochemical performance towards phenol and p-substituted phenol detection was studied with remarkably enhanced oxidation signals at meso-TiO 2 /CPE. The meso-TiO 2 shows considerable surface enhancement effects towards phenols which increase linearly with Hammett’s constants. Additionally at higher NaCl concentrations, the oxidation peak currents of phenols notably increases at meso-TiO 2 /CPE, while remaining unchanged at CPE and nano-TiO 2 /CPE. In summary meso-TiO 2 nanoparticles are superior electrode materials for electrocatalysis.