Through DFT calculations and the finite field approach, it is possible to identify some structural and electronic aspects that could lead to enhancement of the nonlinear optical (NLO) molecular properties of graphene oxide and its derivatives. We proposed a molecular design scheme of NLO response based on push–pull structures. The best NLO models contain –COOH at their edges, acting as electron acceptors, and –OH in the basal plane, acting as an electron donor.