Pt-based multi-metallic electrocatalysts containing hetero-junctions are found to have superior catalytic performance to composition-equivalent counterparts. However, in bulk solution, controllable preparation of Pt-based hetero-junction electrocatalyst is an extremely random work owing to the complexity of solution reactions. Herein, we develop an interface-confined transformation strategy, subtly achieving Au/PtTe hetero-junction-abundant nanostructures by employing interfacial Te nanowires as sacrificing templates. By controlling the reaction conditions, composition-varied Au/PtTe can be easily obtained, such as Au75/Pt20Te5, Au55/Pt34Te11, and Au5/Pt69Te26. Moreover, each Au/PtTe hetero-junction nanostructure appears to be an array consisting of side-by-side Au/PtTe nanotrough units and can be directly used as a catalyst layer without further post-treatment. All Au/PtTe hetero-junction nanostructures show better catalytic activity towards ethanol electrooxidation than commercial Pt/C because of the combining contributions of Au/Pt hetero-junctions and the collective effects of multi-metallic elements, where Au75/Pt20Te5 exhibits the best electrocatalytic performance among three Au/PtTe nanostructures owing to its optimal composition. This study may provide technically feasible guidance for further maximizing the catalytic activity of Pt-based hybrid catalysts.