Carbon-based metal or metal oxide nanocomposites have played an essential role in many fields. In this work, we reported that graphitic-carbon-layer-supported Cu-Cu2O nanocomposites (denoted as Cu-Cu2O-C) can be obtained via calcination of Cu-MOF-74, which shows superior activity for coupling of phenylacetylene to form 1,4-diphenylbutadiyne under visible light because of the synergistic action of the three components in the as-formed Cu-Cu2O-C. The catalyst is highly efficient and can be facilely recycled. Superior to the already reported phenylacetylene coupling systems, only visible light and a very low amount of copper (1.65 mol %) is required in our system. This study provides a promising strategy for visible-light-induced phenylacetylene coupling and highlights the great potential of using metal-organic frameworks as precursors to obtain carbon-supported metal/metal oxide nanocomposites for heterogeneous cooperative catalysis.