The production of value-added chemicals using electrocatalytic CO2 reduction (ECR) is an effective strategy to achieve “carbon neutrality”. However, highly formate-selective production with zinc-based catalysts in ECR systems remains a challenge. In this work, a macroporous hollow nanocage structure was successfully created through the etching of zeolitic imidazolate frameworks (ZIFs) using phytic acid (PA). The surface of the hollow nanocage was then adorned, leading to the formation of a hybrid superstructure product (ZIF-P5/In) with a substantial surface area, enabling effective ECR to formate. The Faraday efficiency of ZIF-P5/In for formate is 80.2 % at −1.26 VRHE. This feasible strategy is expected to provide new insights into the preparation of highly efficient ZIF-derived electrocatalysts.