The interactions between PSS-nBVE copolymers and oppositely charged ionic surfactants (CTAC) in aqueous solution have been investigated using pyrene as a photophysical probe. Static and dynamic fluorescence determinations have been used to obtain information about the microenvironments formed. Micropolarity studies using the I-1/I-3 ratio of the vibronic bands of pyrene show the formation of hydrophobic domains. Early formed premicelles due to the electrostatic interactions between the copolymers and the surfactant (having I-1/I-3 ratios around 1.5-1.6) attract initially the free probes that will migrate from the more aqueous environment to these new hydrophobic sites. The cac's at which these premicelles are formed are found at 0.27 +/- 0.2 mM. Pyrene excimers are detected in the same concentration range. At higher surfactant concentrations free micelles are formed with the same properties of micelles in solutions without polymers, presenting I-1/I-3 ratios around 1.3 and cmc's around 1.45 mM. Also new excimers are formed that disappeared during the progressive addition of the surfactant.