Single-excitation, dual-band-collection toluene planar laser-induced fluorescence (PLIF) is used to measure temperature and number density (or partial pressure) fields in non-uniform supersonic complex flows in the presence of mixing and compressibility. The study provides a quantitative evaluation of the technique in transverse jets in supersonic crossflow (JISCF). It is found that toluene PLIF is highly effective in visualizing the structure of supersonic flows and that temperature can be accurately inferred with acceptable signal-to-noise ratios (of order 30) even when mixing occurs. The technique was applied to several JISCFs that differ by jet fluid properties with resulting different structures. In the presence of compressibility and mixing, it is found that the PLIF signal is non-unique, a feature that is used to identify the mixing region of the transverse jet. Measurement errors due to camera registration errors have also been quantified. Because of the complexity of the flowfield, it is found that minute misalignment (<0.1 pixels) between the two PLIF images can introduce measurable errors on the order of tens of Kelvins and significant errors in temperature gradients.