Complexation. of a hemicyanine-based amphiphile at the air-water interface by polyelectrolytes introduced in the aqueous subphase is shown to be a convenient and effective route to achieve complete deaggregation of the dye chromophores in the Langmuir-Blodgett (LB) film without reducing the chromophore density in the two-dimensional lattice. Enhanced optical second harmonic generation from the LB films of the hemicyanine-polyelectrolyte is demonstrated.