The reductive transformation of Cr(VI) into Cr(III) mediated by formic acid with efficient, stable, and cost-effective catalysts is a promising strategy for remediating Cr(VI) contamination. Herein, we report the facile construction of uniform Co@NC nanosheet-assembled microflowers for the reduction of Cr(VI). Both experimental results and density functional theory (DFT) calculations reveal the vital role of the intensive interfacial electronic interaction between Co nanoparticles and the N-doped carbon layer in facilitating the anchoring and dispersion of Co nanoparticles within the carbon framework. The interfacial electron transfer from Co to NC contributes to the interaction with Cr2O72- ions, promoting the subsequent H-transfer reaction. A Langmuir-Hinshelwood kinetic model has been established for the Cr(VI) reduction catalyzed by the CNCF2 (pyrolyzed at 700 °C), which shows a superior reaction performance. This study provides a facile strategy to delicately design well-assembled heterostructures with rich interfaces and strong interfacial interactions for a series of applications in environmental/thermal catalysis.