Binding polyacrylamide (PAM) with some basic phenothiazine dyes such as methylene blue (MB), toluidine blue (TB) or Azure B (AB) etc. can result in a significant enhancement of resonance Rayleigh scattering (RRS). The maximum RRS wavelengths (lambda(max)) appear at 348, 340 and 342 nm for MB, TB, and AB systems, respectively. Accordingly, a new RRS method for the direct determination of PAM at nanogram levels has been established. The optimum conditions of these reactions, the influencing factors have been investigated. The RRS intensity is directly proportional to the concentration of PAM in the range of 0.040-5.0 mu g/mL for three systems. The methods exhibit high sensitivities, and the detection limits are 15.9 ng/mL for MB system, 44.0 ng/mL for TB system, and 59.8 ng/mL for AB system. The selectivity of the method is investigated by using MB system owing to the highest sensitivity. Concentrations of PAM in tap water, synthetic water and practical waste water samples are determined satisfactorily. The reaction mechanism and RRS enhancement reasons are discussed.