Antimony sulfide (Sb2S3) has attracted much attention due to its great prospect to construct highly efficient, cost-effective, and environment-friendly solar cells. The scalable close-spaced sublimation (CSS) is a well-developed physical deposition method to fabricate thin films for photovoltaics. However, the CSS-processed absorber films typically involve small grain size with high-density grain boundaries (GBs), resulting in severe defects-induced charge-carrier nonradiative recombination and further large open-circuit voltage (VOC) losses. In this work, it is demonstrated that a chemical bath deposited-Sb2S3 seed layer can serve as crystal nuclei and mediate the growth of large-grained, highly compact CSS-processed Sb2S3 films. This seed-mediated Sb2S3 film affords reduced defect density and enhanced charge-carrier transport, which yields an improved power conversion efficiency (PCE) of 4.78% for planar Sb2S3 solar cells. Moreover, the VOC of 0.755V that is obtained is the highest reported thus far for vacuum-based evaporation and sublimation processed Sb2S3 devices. This work demonstrates an effective strategy to deposit high-quality low-defect-density Sb2S3 films via vacuum-based physical methods for optoelectronic applications.