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Ti 2 Cu, TiCu and TiCu 4 were synthesized and their electrocatalytic activities for hydrogen evolution reaction (HER) were investigated. The hydrogen overpotential observed at 10 mA/ cm2 (η 10) followed the order Ti 2 Cu (η 10 = −215 mV) > TiCu (η 10 = −182 mV) > TiCu 4 (η 10 = −170 mV). The hydrogen adsorption energy (∆G Had) on Cu site of TiCu 4 is exergonic and close to optimal position (i.e. ∆G Had = 0). A synergistic effect was proposed to account for the excellent HER performance of these Ti Cu binary intermetallics compounds that could replace PGM and achieve Midas touch in the future. [Display omitted] • High purity of Ti 2 Cu, TiCu and TiCu 4 were synthesized by using rapid arc-melting technique. • Hydrogen evolution reaction (HER) study on Ti 2 Cu, TiCu and TiCu 4 in alkaline media. • HER activity of Ti 2 Cu, TiCu and TiCu 4 were explored by using density functional theory. • Synergistic effect for these Ti Cu binary intermetallics toward HER activity was discussed. [ABSTRACT FROM AUTHOR]