LAUSR

2D polymeric fullerene scaffolds, composed of covalently bonded superatomic C60 nanoclusters, are emerging semiconductors possessing unique hierarchical electronic structures. Hitherto their synthesis has relied on complex and time‐consuming reactions, thereby hindering scalable production and limiting the technological relevance. Here, the study demonstrates a facile electrochemical exfoliation strategy based on the intercalation and expansion of a layered fullerene superlattice, to produce large size (≈52.5 µm2) and monolayer thick 2D polymeric C60 with high exfoliation yield (≈83%). In situ reduction of solvated protons (H+) weakens the interlayer interactions thereby promoting the rapid and uniform intercalation of tetra‐n‐butylammonium (TBA+), ensuring gram‐scale throughput and high structural integrity of exfoliated 2D polymeric C60. As a proof of concept, the solution‐processed 2D polymeric C60 nanosheets have been integrated into thin‐film photodetectors, exhibiting a broad spectral photoresponse ranging from 405 to 1200 nm, with a peak photocurrent at 850 nm and a stable response time. This efficient and scalable exfoliation method holds great promise for the advancement of multifunctional composites and optoelectronic devices based on 2D polymeric C60.