Constructing yolk-shell-structured non-noble-metal composites is very important for improving their activity and stability in catalytic performance. Herein, we report a facile strategy for the synthesis of ternary Cu@SiO2@C yolk-shell composites by converting the resorcinol-formaldehyde (RF) resin-coated Cu2O@SiO2 with a core-shell structure via a thermal treatment under a N-2 atmosphere. Notably, the annealing temperature and silica interlayer play vital roles in modulating their structures and catalytic performance. Moreover, this strategy may pave a new way to constructing non-noble-metal-based composites with yolk-shell structures.