The electro-optical features of functionalized sumanenes with BH, NH, O and S groups is studied theoretically. The effects of substitution on the sumanene CH2 groups with hetero groups are studied using density functional theory computations. Thereafter the multilithiation effect of pristine and heterosubstituted sumanenes are studied to reveal the impact of these modifications on their electro-optical properties. The multilithiation of heterosubstituted sumanenes is an efficient approach to enhance their nonlinear optical response and narrow their highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) energies gaps. The results might open new perspectives for further development of designing novel electro-optical nanomaterials. (C) 2017 Elsevier B.V. All rights reserved.