The exciplex fluorescence technique has been used to separately visualize liquid and vapor phase fuel in engines since its development by Melton. However, as a fluorescence technique it has the potential to be quantitative and the underlying assumptions have been outlined by Melton. An initial quantitative application of the TMPD/naphthalene system, based on these assumptions, applied to a hollow-cone spray in a two-stroke engine, indicated that it substantially over-estimates the concentration of fuel vapor about TDC. The reasons for the discrepancy were investigated and it was concluded that a major factor is the effect of temperature on the photophysics of the species involved. Thus the absorption spectra of the exciplex dopants were determined at temperatures up to 700 K. These experiments showed that the increase in absorption with temperature above 500 K is responsible for the failure of the earlier calibration. Thus quantitative measurements of vapor phase fuel concentration at temperatures above 500 K are only possible if the local gas temperature is known. Other factors, such as selective vaporization of the dopants, and the development of other exciplex systems appropriate for use with gasoline are also discussed.