The use of microscale thin polymer films is widespread in biomedical science and engineering, with applications in areas such as tissue engineering, drug delivery, microfluidic devices, bio-adhesion mediators, and bio-actuators. Much attention is devoted to the use of functional polymers that display stimuliresponsive behavior with the intention of providing "smart" coatings. One potential example is the use of thin thermoresponsive polymer films as drug eluting coatings on medical devices, where not only does the polymer function as a drug reservoir but it also acts as a biocompatibility modulator to improve device performance.Often these thin polymer coatings have to be applied to complex geometries, which can cause problems for in-situ analysis. Another important consideration is the fact that these films have large surface area to mass ratios and thus water uptake can be significant. This is serious because coating stability, device efficacy, and long-term storage are influenced by the physiochemical properties of the polymer which are modulated by water content. Thus, there is a need for a rapid, non-contact, non-destructive, analytical method capable of analyzing thermoresponsive polymers in solution, and in-situ of the solid-state on medical devices. Fluorescence spectroscopy based methods can deal with both sample types and provide additional benefits in terms of high sensitivity and low probe concentrations, which provide for minimal sample disruption. This article gives a brief overview of the application of various fluorescence methods for the physicochemical characterization of thermoresponsive polymers such as poly (N-isopropylacrylamide), PNIPAm.