In this study, a novel electrocatalyst, namely Cu/N-pg-C derived from Cu-doped ZIF-8, was investigated for making syngas products with various H2/CO ratios. Different ratios of the electrocatalytic syngas products CO and H2 could be selected by adjusting the applied potential and hence tuning the transfer of electrons from N-doped graphitic carbon to the well-dispersed Cu nanoclusters.