AbstractHeteroatom‐doped peri‐acenes (PAs) have recently attracted considerable attention considering their fascinating physical properties and chemical stability. However, the precise sole addition of boron atoms along the zigzag edges of PAs remains challenging, primarily due to the limited synthetic approach. Herein, we present a novel one‐pot modular synthetic strategy toward unprecedented boron‐doped PAs (B‐PAs), including B‐[4,2]PA (1 a‐2), B‐[4,3]PA (1 b‐2) and B‐[7,2]PA (1 c‐3) derivatives, through efficient intramolecular electrophilic borylation. Their chemical structures are unequivocally confirmed with a combination of mass spectrometry, NMR, and single‐crystal X‐ray diffraction analysis. Notably, 1 b‐2 exhibits an almost planar geometry, whereas 1 a‐2 displays a distinctive bowl‐like distortion. Furthermore, the optoelectronic properties of this series of B‐PAs are thoroughly investigated by UV/Vis absorption and fluorescence spectroscopy combined with DFT calculation. Compared with their parent all‐carbon analogs, the obtained B‐PAs exhibit high stability, wide energy gaps, and high photoluminescence quantum yields of up to 84 %. This study reveals the exceptional ability of boron doping to finely tune the physicochemical properties of PAs, showcasing their potential applications in optoelectronics.