Transition metal tellurides have drawn much interest as alternative electrocatalysts for the oxygen evolution reaction (OER) on account of the high electrical conductivity and variable phase and composition. However, they suffer from the low exposure of active sites and unfavourable adsorption energies of oxygenated intermediates, exhibiting a limited catalytic activity. Herein, one-dimensional hetero-structured NiFeCo–OH/NiTe nanorod arrays with amorphous/crystalline interfaces are constructed on a nickel foam scaffold (denoted as NiFeCo–OH/NiTe@NF) through a facile hydrothermal method followed by a rapid electrodeposition process. Both the experimental investigations and density functional theory (DFT) calculations reveal that the heterostructure with amorphous/crystalline interfaces not only provides abundant defects and disordered arrangement for high exposure of active sites but also optimizes the electronic structure for energetically favourable intermediates. Accordingly, the as-developed NiFeCo–OH/NiTe@NF exhibits an excellent electrocatalytic performance for the OER with a low overpotential of 276 mV at a current density of 100 mA cm⁻² in 1.0 M KOH and a remarkable stability. This study may pave a new avenue for the optimal design and construction of highly efficient transition metal telluride-based electrocatalysts for the OER.