A versatile method to remove a broad spectrum of dye pollutants from wastewater rapidly and efficiently is highly desirable. Here, we report that the complex coacervation of cationic trimeric imine-based surfactants (TISn) with negatively charged hydrolyzed polyacrylamide (HPAM) can be used for this purpose. The coacervation occurs in a wide concentration and composition range and requires the HPAM and TISn concentrations as low as 0.1 g/L and 0.1 mM, respectively. Dye effluents treated by trimeric surfactants and HPAM complete phase separation within 30 s under turbulent conditions, which generates an exceedingly small volume fraction (0.4%) of viscoelastic coacervate and a clear supernatant with a dye removal efficiency of up to 99.9% for anionic and neutral dyes in dosages of up to 120 mg/L. Crowded molecular arrangement and thick framework in coacervate are responsible for the rapid phase separation rate and low volume fraction. The trimeric imine surfactant/polymer coacervation provides a simple, effective, and sustainable approach for the rapid removal of dyes and other organic pollutants.