In the modern DC electrical transmission system, high-energy photons interact with silicone rubber (SIR) chains during long-term ultraviolet (UV) irradiation, it degrades the surface properties and triggers surface discharge (flashover) along the SIR-air interface, threatening the secure operation of the advanced electrical equipment. To further comprehend how UV-aging influences the flashover performance, in this work, the chemical bonds, surface charge transport parameters, and flashover performance of UV-aged SIR samples are characterized, and the influence mechanisms of UV-aging on surface discharge in dry and humid air are comprehensively clarified through the investigation from “molecular-mesoscopic-macroscopic” scales. The results indicate both degradation and oxidization reactions occur during UV-aging. The degraded molecular chains dominate the discharge in dry air, while oxidization reactions determine the discharge in humid environment: The degradation reactions reduce the surface trap depth and increase surface conductivity, leading to large surface leakage current and surface charge dissipation rate, causing flashover voltage in dry air increases and decreases as UV-aging time increasing. The oxidization of the chains introduces –OH and –COOH groups into chains, enhancing permittivity and adsorbing H2O molecules, significantly increasing surface leakage current, causing surface discharge voltage in humid air to decrease as UV-aging time increases.