To investigate the characteristics of photosynthetic physiological changes in leaves of Mangifera indica L. cv. Guifei under enhanced ultraviolet (UV)-B radiation, natural light-exposed trees were used as controls and 96 kJ·m−2·d−1 enhanced UV-B radiation was artificially simulated in the field. The changes in fruit maturity and quality, the leaf net photosynthetic rate (Pn), photosynthetic pigment contents, photochemical reactions, the activities of photosynthetic enzymes and related gene expression levels were determined. Compared with the control, the percentage of mature fruits under the treatment significantly increased, and fruit quality improved. The net photosynthetic rate (Pn), photosynthetic pigment content, Hill reaction activity, and photochemical quenching coefficient (qP) of the treated leaves showed significantly higher values than those of the control leaves. The activities of Rubisco and Rubisco activating enzyme (RCA) and the expression levels of the Rubisco large subunit and Rubisco small subunit were significantly increased. Treatment with 96 kJ·m−2·d−1 enhanced ultraviolet-B radiation improved Rubisco activity by increasing the expression of the Rubisco large and small subunit genes, thereby enhancing the CO2-fixing capacity and dark reaction capacity of leaves. Thus, the net photosynthetic rate of leaves increased, which promoted the early maturity of ‘Guifei’ mango by the rapid accumulation of photosynthetic products.