Imide-modified polycyclic aromatic hydrocarbons can be widely applied in the field of optoelectronic materials. In this work, we have synthesized four novel functionalized benzopicenes and characterized their solid structures and optoelectronic properties. The fluorescence of the four functionalized benzopicenes showed red shifts with increasing solvent polarity; the quantum yields are high in the solution state and moderate in the solid state. The single crystal structures show that the benzopicenes adopt a lamellar motif π-stacking. Their good solubility and optoelectronic properties make them potential solution-processable candidates for organic devices, bioimaging and biolabeling.