Rh-0/CeO2 catalystwas prepared by the reduction of Rh+3 ions on CeO2 surface and characterized by transmission electron microscopy, inductively coupled plasma optical emission spectrometry, X-ray photoelectron spectroscopy and powder X-ray diffractometry techniques. To investigate its electrocatalytic activity for H-2 evolution reaction, a glassy carbon electrode (GCE) was modified with Rh-0/CeO2. The modified electrode was found to exhibit a high electrocatalytic activity (turnover frequency (TOF): 1.56 s(-1) at j = 100 mA.cm(-2)) with a small Tafel slope of 34 mV.dec(-1). Moreover, a high exchange current density of 0.527 mA.cm(-2) and low overpotential of 42 mV at j = 10 mA.cm(-2) were also obtained using Rh-0/CeO2-GCE. There is no noticeable change in the Tafel slope and eta(10) values even after 10000 cyclic scans in acidic environment at room temperature, which makes Rh-0/CeO2 on GCE highly durable and long lived electrocatalyst for water splitting. (C) 2019 The Electrochemical Society.