Two novel helicene-like molecules based on naphthotetrathiophene are successfully synthesized. All target molecules and intermediates are characterized by (1)H NMR, (13)C NMR, IR, and HRMS. Their electrochemical and photophysical properties are studied. The configurations of the molecules are optimized by DFT quantum calculations and UV-vis behaviors are also predicted to further understand the origin of different absorption bands. We believe the current work illustrated an efficient way for the design and synthesis of sophisticated structures with naphthotetrathiophene as building blocks.