In this paper, an experimental study of R1234yf replacing R22 in window air conditioning was carried out. The optimum types of capillary tubes and the charge amount were obtained, and the system performance of the window air conditioning charged with R1234yf was tested in an air conditioner performance teat facility under nominal and high-temperature conditions. The results revealed that the cooling capacity and coefficient of performance (COP) of the air conditioner charged with R1234yf were 28.5% and 11.1%, respectively, under nominal conditions, which were lower than that of R22. Under high-temperature conditions, the cooling capacity of R1234yf was still lower than that of R22, but the COP was slightly higher. This suggests that R1234yf may be a suitable substitution for R22 in high-temperature environment.