Copolymers of [2-(acryloyloxy)ethyl]trimethylammonium chloride (AETAC) and acrylamide (AAm) (AETAC-co-AAm) are polyelectrolytes used as flocculants in wastewater purification. Diffusion-ordered two-dimensional NMR spectroscopy (DOSY) experiments for AETAC-co-AAm samples with Mw ranging from 1.9 to 3.9 million and a polyacrylamide sample with Mw of 1.3 million were carried out in pure D2O and in D2O containing 0.1 or 1 M NaCl using an inverse-geometry diffusion probe system. Projections of the DOSY contour plots onto the diffusion coefficient (D) dimension gave distributions of D for the AETAC and AAm units in the samples. The D values at the maximum point of the distribution (Dp) agreed fairly well with those determined by dynamic light scattering.