Deoxyribonucleic acid (DNA) and a self-doped conjugated polyelectrolyte, poly (4-(2,3-dihydrothieno[3,4-b]- [1,4]dioxin-2-yl-methoxy)-1-butanesulfonic acid (PEDOT-S), are assembled for organic optoelectronics and bioelectronics. The DNA's helix−coil phase transition in water is studied as a function of composition by thermo-optical analysis. DNA and PEDOT-S are functionalized by using a surfactant, cetyltrimethylammonium chloride (CTMA), and DNA:CTMA, PEDOT-S:CTMA, and DNA:CTMA:PEDOT-S:CTMA complexes were characterized regarding thermal, optical, morphological, and structural properties. Finally, DNA and DNA:PEDOT-S mixtures are processed in water for fabricating organized films through brushing. The electrical properties of these films are characterized using an interdigitated electrode. The films show an electronic conductivity of ∼10 −6 −10 −5 S/cm in a range of semiconductors.