Electron donating carbazole and triphenylamine derivatives are widely used in molecular electronic materials and in biological fluorescent or active probes. Novel easy-to access, highly substituted, electron-rich carbazole and triphenylamine compounds were designed, synthesized and characterized in photophysical and electrochemical experiments. These compounds, with an unusual D-π-D-π-D molecular design are based on carbazole and triphenylamine cores, thiophene conjugated linker and donor aromatic extremities. They showed excellent light-absorbing and emitting properties with high fluorescent quantum yield along with low oxidation potential and excellent electron donating properties. Computational calculations complete the experimental data, and enlighten about the redox and photophysical processes.