This study examined the photosynthetic responses of two sunflower hybrids to elevated temperatures and excess light intensity in the flowering stage by measuring the chlorophyll a fluorescence (ChlF) under morning and afternoon field conditions to determine the photosynthetic pigment contents and the relative accumulation of photosynthetic proteins. The morning environmental conditions were considered optimal, while the afternoon was characterised by elevated temperatures and excess light intensity. The minimum fluorescence intensity (F0), the electron-flux-reducing end electron acceptors at the photosystem I acceptor side per reaction centre (RE0/RC), and the D1 protein had significant, high, and positive correlations with the environmental conditions, which indicates that they were the most useful in the sunflower-stress-response research. In hybrid 7, the elevated temperatures and the excess light intensity resulted in the inactivation of the oxygen-evolving complex, which was indicated by the positive L, K, and J steps, the increase in the maximum quantum yield of PSII (TR0/ABS), the decrease in the electron transport further than the primary acceptor QA (ET0/(TR0-ET0)), the reduction in the performance index (PIABS), and the higher relative accumulation of the light-harvesting complex of the photosystem (LHCII). Hybrid 4 had smaller changes in the fluorescence curves in phases O–J and J–I, and especially in steps L, K, J, and I, and a higher PIABS, which indicates a more efficient excitation energy under the unfavourable conditions. As the tested parameters were sensitive enough to determine the significant differences between the sunflower hybrids in their photosynthetic responses to the elevated temperatures and excess light intensity in the flowering stage, they can be considered useful selection criteria. The development of more adaptable sunflower hybrids encourages sustainable sunflower production under stressful growing conditions.