Fluorescence techniques, including quenching and anisotropy measurements, have been used to study the dynamic behavior of poly(N,N-dimethylacrylamide) (PDMAC) in both dilute methanolic and aqueous solution, respectively. These studies indicate that the polymer exists as a flexible and relatively open coil in aqueous media whose behavior is largely unaffected by changes in pH. Preliminary time-resolved anisotropy measurements reveal that complexation with poly(methacrylic acid) (PMAA) produces a relatively rigid species in which the segmental mobility of the PDMAC is dramatically reduced.