Two-dimensional semiconductors exhibit strong light emission under optical or electrical pumping due to quantum confinement and large exciton binding energies. The regulation of the light emission shows great application potential in nextgeneration optoelectronic devices. Herein, by the physical vapor deposition strategy, we synthesize monolayer hexagonal-shaped WS 2 , and its photoluminescence intensity mapping show three-fold symmetric patterns with alternating bright and dark regions. Regardless of the length of the edges, all domains with Sterminated edges show lower photoluminescence intensity, while all regions with W-terminated edges exhibit higher photoluminescence intensity. The photoluminescence segmentation mechanism is studied in detail by employing Raman spectroscopy, atomic force microscopy, high-resolution transmission electron microscopy, and Kelvin probe force microscopy, and it is found to originate from different strain distributions in the S-terminated region and the W-terminated region. The optical band gap determined by the photoluminescence in the dark region is ∼2 meV lower than that in the bright region, implying that more strain is stored in the S-terminated region than in the W-terminated region. The photoluminescence segmentation vanishes in transferred hexagonal-shaped WS 2 from the initial substrate to a fresh silicon substrate, further confirming the physical mechanism. Our results provide guidance for tuning the optical properties of two-dimensional semiconductors by controllable strain engineering.