Search for simple and economical electrocatalyst for the hydrogen gas evolution reaction (HER), which can resemble to the performance of Pt and other precious metals, is a challenging research interest. In this work, a systematic effect of pre-treatment potential of screen-printed carbon (SPCE) surface on the HER performance in 0.5 M H2SO4 was carried out. A new observation of a low potential HER (onset potential, E onset = −0.02 V vs. RHE) at a cathodic potential, −0.5 V vs. Ag/AgCl on 1 hr pre-treated screen-printed carbon electrode (SPCE*, * = pre-treated) was observed. Physicochemical and electrochemical characterizations of the SPCE* by field emission scanning electron-microscope, Raman, IR and X-Ray photoelectron spectroscopes reveals specific generation of carboxylic acid functionalized carbon surface and in turn for the enhanced HER on the modified electrode surface. Electrochemical characterization of SPCE* with Fe(CN)6 3− support the observation. A marked decrement in the peak current and significant increase in the peak-to-peak separation potential response due electrostatic repulsion between the anion sites of Fe(CN)6 3− and –COO– were noticed. This observation is in parallel with the reduced electrical double layer capacitance value of the SPCE* system. The E onset and Tafel value (54.7 mV dec−1) obtained here are comparable to those at Pt, MoS2, MoSe2 and superior over the N- and P-doped graphene/carbon electrocatalysts for HER. A prototype HER system was developed and demonstrated for H2 gas production at a rate of 0.0053 μM s−1 (Operating potential = −0.5 V vs Ag/AgCl), which is comparable to that of precious metal and metal compound electrocatalysts based HER performance.