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Ti/ML-TNT/HRP/Nafion© sensor device is fabricated using TiO2 multileg nanotubes (ML-TNT). This device is used for photoelectrochemical enzymatic detection of hydrogen peroxide for different concentrations and the electrochemical surface phenomenon was studied using electrochemical impedance spectroscopy. The device shows a photo-induced enhancement of biosensing performance towards increasing concentration of the analyte, which is analyzed with cyclic voltammetry and enzyme kinetics. The non-turn over condition cyclic voltammetry shows reversible one-electron transfer reaction due to Fe2+/3+ reaction of the heme co-factor while the turn over shows two electrons reaction because of the reduction of H2O2. Further analysis shows an enhanced sensitivity of 3.302 mA/mM.cm2, selectivity towards H2O2, range of detection 41.2 × 10−9– 6.0 × 10−3 M and limit of detection 12.0 × 10−9 M. The limitation of this electrode towards high concentration of H2O2 is analysed with Michaelis-Menten fit of the enzymatic reaction and Randles circuit of electrochemical impedance spectra.