The organization of conjugated polyelectrolytes (CPEs) interacting with biomolecules sets conditions for the biodetection of biological processes and identity, through the use of optical emission from the CPE. Herein, a well-defined CPE and its binding to DNA is studied. By using dynamic light scattering and circular dichroism spectroscopy, it is shown that the CPE forms a multimolecule ensemble in aqueous solution that is more than doubled in size when interacting with a small DNA chain, while single chains are evident in ethanol. The related changes in the fluorescence spectra upon polymer aggregation are assigned to oscillator strength redistribution between vibronic transitions in weakly coupled H-aggregates. An enhanced single-molecule spectroscopy technique that allows full control of excitation and emission light polarization is applied to combed and decorated lambdaDNA chains. It is found that the organization of combed CPE-lambdaDNA complexes (when dry on the surface) allows considerable variation of CPE distances and direction relative to the DNA chain. By analysis of the polarization data energy transfer between the polymer chains in individual complexes is confirmed and their sizes estimated.