Making use of the reflected ultraviolet (UV) radiation with a reflective inner wall is a promising way to improve UV reactor performance. In this study, the impact of inner-wall reflection on UV reactor performance was evaluated in annular single-lamp UV reactors by using computational fluid dynamics, with an emphasis on the role of diffuse reflection. The UV radiation inside the reactor chamber was simulated using a calibrated discrete ordinates radiation model, which has been proven to be a reliable tool for modeling fluence rate (FR) distributions in UV reactors with a reflective inner wall. The results show that UV reactors with a highly reflective inner wall (Reflectivity = 0.80) had obviously higher FRs and reduction equivalent fluences (REFs) than those with an ordinary inner wall (Reflectivity = 0.26). The inner-wall diffuse reflection further increased the reactor REF, as a result of the elevated volume-averaged FR. The FR distribution uniformity had conditioned contributions to UV reactor performance. Specifically, in UV reactors with a plug-like flow the FR distribution uniformity contributed to the REF to some extent, while in UV reactors with a mixed flow it had little influence on the REF. This study has evaluated, for the first time, the impact of inner-wall diffuse reflection on UV reactor performance and has renewed the understanding about the contribution of FR distribution uniformity to UV reactor performance.