Two-dimensional (2D) nanomaterials have recently attracted considerable attention due to their promising applications in next-generation electronics and optoelectronics. In particular, the large-scale synthesis of high-quality 2D materials is an essential requirement for their practical applications. Herein, we demonstrate the wafer-scale synthesis of highly crystalline and homogeneous monolayer WS2 by an enhanced chemical vapor deposition (CVD) approach, in which precise control of the precursor vapor pressure can be effectively achieved in a multi-temperature zone horizontal furnace. In contrast to conventional synthesis methods, the obtained monolayer WS2 has excellent uniformity both in terms of crystallinity and morphology across the entire substrate wafer grown (e.g., 2 inches in diameter), as corroborated by the detailed characterization. When incorporated in typical rigid photodetectors, the monolayer WS2 leads to a respectable photodetection performance, with a responsivity of 0.52 mA/W, a detectivity of 4.9 × 109 Jones, and a fast response speed (< 560 μs). Moreover, once fabricated as flexible photodetectors on polyimide, the monolayer WS2 leads to a responsivity of up to 5 mA/W. Importantly, the photocurrent maintains 89% of its initial value even after 3, 000 bending cycles. These results highlight the versatility of the present technique, which allows its applications in larger substrates, as well as the excellent mechanical flexibility and robustness of the CVD-grown, homogenous WS2 monolayers, which can promote the development of advanced flexible optoelectronic devices.