Main features of polymers as supports for spectral measurements are summarized. Spectral characteristics of selected singlet and triplet probes, such as absorption and emission maxima, quantum yield and lifetime of emission, their anisotropy and energy transfer, are evaluated with respect to their use in common polymer matrices. Photophysical processes of 3-substituted coumarin derivatives are analyzed and their suitability for application as singlet probes in polymer matrices is evaluated.