Traditional working fluids used in direct vapor generation for solar organic Rankine cycle (DVG-ORC) systems have a high global warming potential (GWP), making it imperative to find environmentally friendly alternative working fluids for these systems. This paper evaluates the performance of the DVG-ORC system under different operating conditions. By comparing the results of traditional working fluids with those of low-GWP fluids, the feasibility of using low-GWP fluids as alternative working fluids is explored. Additionally, to screen the working fluids suitable for this system further, the system is optimized with net output power as the objective function. The results show that evaporation temperature has different impacts on system performance. R245ca and R1336mzz(Z) exhibit higher net output power at different evaporation temperatures, with R1336mzz(Z) only reducing it by 3.73–5.26% compared to R245ca. However, an increase in condensation temperature negatively affects system performance, leading to a decrease in net output power and various efficiencies. Net output power increases with an increase in mass flow rate, indicating that higher mass flow rates can enhance system performance. The optimization results show that the net output power of low-GWP working fluid R1336mzz(Z) decreases by only 3.44% compared to R245ca, which achieves the maximum net output power. Moreover, among low-GWP working fluids, R1336mzz(Z) demonstrates the highest ORC efficiency and system efficiency, making it the most suitable working fluid for the DVG-ORC system due to its environmental friendliness and safety.