Potassium (K) deficiency significantly decreases photosynthesis due to leaf chlorosis induced by accumulation of reactive oxygen species (ROS). But, the physiological mechanism for adjusting antioxidative defense system to protect leaf function in maize (Zea mays L.) is unknown. In the present study, four maize inbred lines (K-tolerant, 90-21-3 and 099; K-sensitive, D937 and 835) were used to analyze leaf photosynthesis, anatomical structure, chloroplast ultrastructure, ROS, and antioxidant activities. The results showed that the chlorophyll content, net photosynthetic rate (Pn), stomatal conductance (Gs), photochemical quenching (qP), and electron transport rate of PSII (ETR) in 90-21-3 and 099 were higher than those in D937 and 835 under K deficiency treatment. Parameters of leaf anatomical structure in D937 that were significantly changed under K deficiency treatment include smaller thickness of leaf, lower epidermis cells, and vascular bundle area, whereas the vascular bundle area, xylem vessel number, and area in 90-21-3 were significantly larger or higher. D937 also had seriously damaged chloroplasts and PSII reaction centers along with increased superoxide anion (O2−) and hydrogen peroxide (H2O2). Activities of antioxidants, like superoxide dismutase (SOD), catalase (CAT), and ascorbate peroxidase (APX), were significantly stimulated in 90-21-3 resulting in lower levels of O2− and H2O2. These results indicated that the K-tolerant maize promoted antioxidant enzyme activities to maintain ROS homeostasis and suffered less oxidative damage on the photosynthetic apparatus, thereby maintaining regular photosynthesis under K deficiency stress.