The complex formation between sodium carboxymethylcellulose (NaCMC) and dodecyltrimethylammonium bromide (DTAB) at various sodium bromide concentrations (C-NaBr) has been studied by microcalorimetry, turbidimetric titration, steady-state fluorescence measurements, and the fluorescence polarization technique. The addition of salt is found to influence the formation of NaCMC/DTAB complexes markedly. At C-NaBr = 0.00, 0.01, 0.02, 0.10, and 0.20 M, DTAB monomers form micelle-like aggregates on NaCMC chains to form NaCMC/DTAB complexes above the critical surfactant concentration (C-1). At C-NaBr, = 0.23 M, DTAB molecules first form micelles above a 2.46 mM DTAB concentration prompted by the added salt, and then, above C-1 = 4.40 mM, these micelles can aggregate with NaCMC chains to form NaCMC/DTAB complexes. However, at C-NaBr, = 0.25 M, there is no NaCMC/DTAB complex formation because of the complete salt screening of the electrostatic attraction between DTAB micelles and NaCMC chains. It is also surprisingly found that the addition of NaBr can bring out a decrease in C-1 at C-NaBr < 0.20 M. Moreover, the addition of NaBr to a mixture of 0.01 g/L NaCMC and 3.6 mM DTAB can directly induce the formation of NaCMC/ DTAB complexes. This salt-enhancing effect on the complex formation is explained as the result of competition between the screening of interaction of polyelectrolyte with surfactant and the increasing of polyelectrolyte/ surfactant interaction owing to the growth of micelles by added salt. When the increasing of polyelectrolyte/ surfactant interaction exceeds the screening of interaction, the complex formation can be enhanced.