Emeraldine Hydrochloride salt is coated on copper substrate and studied for hydrogen storage and hydrogen evolution reaction in 1 M NaOH. Phenomenological thermodynamic approach demonstrated elsewhere in conjunction with the cyclic voltammetry data is employed to calculate the solvent modified work function for polyaniline coated copper in alkaline medium as −0.65 eV. The solvated work function is in satisfactory agreement with the band gap difference of π−π* transition in emeraldine base and π- polaron transition in emeraldine salt ca −0.6 eV as reported in the literature. 13C and 1H NMR studies revealed that polyaniline undergoes switching between emeraldine salt and emeraldine base, before and after hydrogen evolution respectively. The volume of hydrogen evolved on polyaniline coated copper is 1.64 times than that on copper as demonstrated by Gas chromatography. Thus emeraldine salt, when stored in NaOH act as hydrogen storage medium and upon electrochemical perturbation can release hydrogen at controlled rate depending on the scan rate employed. © 2017 Hydrogen Energy Publications LLC