Graphene nanoribbons (GNRs), quasi-one-dimensional strips of graphene, exhibit a nonzero bandgap due to quantum confinement and edge effects. In the past decade, different types of GNRs with atomically precise structures have been synthesized by a bottom-up approach and have attracted attention as a novel class of semiconducting materials for applications in electronics and optoelectronics. We report the large-scale, inexpensive growth of high-quality oxygen–boron–oxygen-doped chiral GNRs with a defined structure using chemical vapor deposition. For the first time, a regular 2D self-assembly of such GNRs has been demonstrated, which results in a unique orthogonal network of GNRs. Stable and large-area GNR films with an optical bandgap of ∼1.9 eV were successfully transferred onto insulating substrates. This ordered network structure of semiconducting GNRs holds promise for controlled device integration.