This work investigates the spray combustion of Jet-A fuel in an optical constant-volume combustion chamber under different ambient initial conditions. Ambient temperature was varied at 800K, 1000K, and 1200K and five different ambient O2 concentrations were used, spanning 10–21%. These ambient conditions can be used to mimic practical diesel engine working conditions under different fuel injection timings and exhaust gas recirculation (EGR) levels. Both transient and quasi-steady state analyses were conducted. The transient analysis focused on the flame development from the beginning to the end of the combustion process, illustrating how the flame structure evolves with time. The quasi-steady state analysis concentrated on the stable flame structure and compared the flame emissions in terms of spatially integrated intensity, flame effective area, and intensity per pixel. The transient analysis was based on measurements using high-speed imaging of both OH∗ chemiluminescence and broadband natural luminosity (NL). For the quasi-steady state analysis, three flame narrow-band emissions (OH∗ at 310nm, Band A at 430nm and Band B at 470nm) were captured using an ICCD camera. Based on the current Jet-A data and diesel data obtained from previous experiments, a comparison between Jet-A and diesel was made in terms of flame development during the transient state and spatially integrated intensity, flame effective area, and intensity per pixel during the quasi-steady state. For the transient results, Jet-A shares a similar flame development trend to diesel, but featuring a narrower region of NL and a wider region of OH∗ with the increase of ambient temperature and O2 concentration. The soot cloud is oxidized more quickly for Jet-A than diesel at the end of combustion, evident by comparing the area of NL, especially under high O2 concentration. The quasi-steady state results suggest that soot is oxidized effectively under high O2 concentration conditions by the wider region of OH∗ in the downstream locations where only OH∗ emission is observed. The intensity of OH∗ is higher for Jet-A than diesel under low O2 concentration but lower under high O2 concentration. The intensity of NL is higher for Jet-A for all the conditions investigated. However, the intensities of Band A and Band B are lower for Jet-A for all these conditions. Based on the imaging of multiple-band flame emissions, the spray flame structures were further analyzed for the two fuels under both low temperature and conventional combustion modes. Conceptual flame structures were proposed to complement the previous conceptual models for spray combustion under different combustion modes.