This study was designed to investigate the effects of exogenous calcium on the tolerance of Rosa hybrida ‘Carolla’ to high-temperature and the physiological mechanisms underlying this response. Leaves of ‘Carolla’ grown under stress were treated by spraying four different concentrations of calcium chloride (CaCl2; 50, 100, 150, or 200 μM). The photosynthetic responses, antioxidant enzyme activities, and osmotic substance contents were measured under high-temperature stress at the flowering stage. Temperature-stressed ‘Carolla’ with CaCl2 treatment showed significantly increased chlorophyll (Chl) content, net photosynthetic rate (An), transpiration rate (E), stomatal conductance (gs), water use efficiency (WUE), superoxide dismutase (SOD), peroxidase (POD), and ascorbate peroxidase (APX) activities together with proline (Pro), soluble sugar (SS), and soluble protein (SP) concentrations, while malonaldehyde (MDA) content and relative electrical conductivity (REC) were significantly reduced. The damages caused by high-temperature stress were alleviated by applying CaCl2. Among the CaCl2 treatments, 100 μM CaCl2 best minimized the damage caused by high-temperature to ‘Carolla’. This study showed that exogenous calcium could improve the tolerance of Rosa hybrida ‘Carolla’ to high-temperature stress by regulating photosynthesis, the antioxidant system, and osmotic substances.