The use of fluorescence spectroscopy in the study of associative phenomena is illustrated . The use of standard global of and global compartmental analysis in a number of complex systems is clearly shown. Association between detergent molecules and between detergents and polymers was analysed and the different parameters characterising such an interaction evaluated. Associative phenomena in covalent polymers such as dipole-dipole interactions in halato-telechelic polymers and in syndiotactic polymethylmethacrylate were investigated. The rate constants of inter and intramolecular interactions in halato-telechelic polymer were determined through a systematic analysis of the different interactions using global tricompartmental analysis of fluorescence decays combined with a scanning technique to estimate the rate constants. Fluorescence polarization and changes in fluorescence decay times in the temperature range of gelation reveal a stepwise mechanism in the gelation of s-PMMA.