A polymer–surfactant micellar complex has been studied as a fluorescence resonance energy transfer (FRET) donor to fluorescein‐labeled DNA (ssDNA‐Fl). In water, the molar absorptivity and fluorescence quantum efficiency of cationic poly(fluorene‐co‐phenylene) (c‐PFP) are substantially increased in the presence of non‐ionic surfactants. A TEM microscopic study shows the formation of a nanowire micellar complex of c‐PFP and the surfactants. About a 400% enhancement of the FRET signal is measured in c‐PFP/ssDNA‐Fl with Brij 30, relative to that without surfactants. The signal amplification is successfully modulated using different types of non‐ionic surfactants which perturb the complexation, fine‐structure of the complex (i.e., donor‐acceptor separation), and the resulting energy transfer process.