Although transition metal sulfides have presented prospect in electrochemical sensing, their electrocatalytic performance still cannot meet the demands for practical applications due to the difficulties in mass transport and electron transfer. In this work, double-shelled CuS nanocages (2-CuS NCs) were prepared for enzyme-free ascorbic (AA) sensor through a Cu 2 O-templated method. The unique double-shelled hollow structure displayed large specific surface areas, ordered diffusion channels, increased volume occupying rate, and accelerated electron transfer rate, resulting in enhanced electrochemical dynamic. As a sensing electrode for AA, 2-CuS NCs modified glassy carbon electrode (2-CuS NCs/GCE) exhibited eminent electrocatalytic activity in terms of satisfying sensitivity (523.7 μA mM −1 cm −2 ), short response time (0.31 s), and low limit of detection (LOD, 0.15 μM). 2-CuS NCs look promising for analytical sensing of AA in electrochemical sensors thanks to its prominent electrocatalytic kinetics issued from double-shelled hollow porous structure.