Here, we report template‐assisted assembly of emissive carbon quantum dot (CQD) microcrystals on organized cellulose nanocrystals templates at the liquid–air interface. This large‐scale assembly is facilitated by the complementary amphiphilic character of CQDs and cellulose nanocrystals in the organized nematic phase. The resulting large microcrystals up to 200 μm across show unusually high emission that is not observed for limited CQDs aggregates. The dense crystal packing of CQDs in the layered fashion suppresses local molecular rotations and vibrations, thus restricting the intermolecular energy transfer and corresponding quenching phenomena. The as‐prepared crystals are mechanically stable and can be exploited for recyclable catalysis, enabling applications beyond the individual nanoparticles or disordered aggregates. The ligand‐templated assembly can be used to diversify CQD crystal architectures to guide formation of fibers, microplates, and micro‐flowers. The template‐assisted assembly of large and emissive carbon quantum dot (CQD) microcrystals using organized amphiphilic cellulose nanocrystals (CNCs) at the liquid–air interface is presented. This large‐scale assembly is facilitated by the complementary amphiphilic interactions of CQDs and CNCs in an organized nematic phase.