Crystallization‐Induced Multiple Band Luminescence Exhibiting Whitish Color of Bpin‐Appended Naphtho[1,2‐C:5,6‐C′]bis[1,2,5]oxadiazole

π‐Conjugated molecules with highly π‐extended structures are important for optoelectronic applications. Naphthobischalcogendiazole backbones are recently developed electron‐accepting π‐extended structures. Herein, we report the discovery of a whitish luminescence based on the appearance of multiple PL bands for boronate pinacol ester (Bpin)‐appended naphtho[1,2‐c:5,6‐c′]bis[1,2,5]oxadiazole ( NOz ) crystal. The appearance of these multiple PL bands was interpreted by the close packing of PB2‐NOz , which was likely assisted by intermolecular short contacts involving the Bpin units. This discovery suggests that the strong intermolecular interaction by Bpin can be exploited for the crystal engineering toward versatile optoelectronic functions, rather than being used solely as conventional building blocks in coupling reactions.