The properties of synthesized ambipolar organic semiconductor (OSC) materials, containing hydrogen bonding, i.e. the 6,6′-dibromoindigo and the three s-indaceno [1, 2-b:5, 6-b′] dithiophene-4,9-dione derivatives, have been systematically studied using a density functional theory. The hydrogen bonding formed between the interlayer molecules, though it does not affect the charge mobility in the same layer, influences the interorbital overlapping of HOMO and LUMO states between the layers, and influences the charge mobility directly. In addition, the hydrogen bonding between the layers may reinforce the π-π stacking and make the center-to-center distance closer, which indirectly enhances charge mobility, and can turn a monopole OSC into an ambipolar one. [ABSTRACT FROM AUTHOR]