We describe the design and modular synthesis of a library of substituted hexabenzoovalene derivatives (SHBO), along with the key precursor dinaphthopyrenes (3), highlighting the influence of a wide array of substituent variation on the photophysical properties via UV-vis absorption, fluorescence spectra and electrochemical methods. The results show that the cyclized hexabenzoovalenes present a stronger spectroscopic red-shift than the corresponding dinaphthopyrenes. X-ray diffraction analysis suggests that intermediate 3hx containing two nitro groups forms a trans-configuration with twisted structures. Our systematic investigation might provide a realistic design strategy to construct large one-dimensional and two-dimensional materials via bottom-up approaches.