Graphdiyne nanoribbons with high chemical precision are of great significance for further understanding of the intrinsic properties of graphdiyne and the relationship between structure and properties. However, the reliable synthesis of graphdiyne nanoribbons with chemical precision remains a significant challenge. A facile method is now presented for fabrication of graphdiyne nanoribbons with uniform width through stepwise inter‐ and intramolecular Glaser–Hay coupling reaction of ethynyl groups. The synthetic ribbons were interwoven into nanotextiles by π–π stacking and were applied for protective coating of Li‐electrode in Li‐ion batteries, which efficiently suppressed the growth of the Li dendrites during cycling and prolonged the life span of Li‐metal batteries.

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