The present work aims to study the effect of solvent as well as arrangement of donor-acceptor groups on linear and non-linear optical (NLO) response properties of two experimentally studied intramolecular charge-transfer (ICT)-based fluorescent sensors. One of them (molecule 1) is a donor-acceptor (D-A) system with hemicyanine and dimethylanilino as electron withdrawing and donating groups, respectively, while the other one (molecule 3) is molecule 1 fused with a boron-dipyrromethene (BODIPY) moiety. BODIPY acts as the electron acceptor group of molecule 2 that as well consists of dimethylanilino as the electron donor. Density functional theory (DFT) as well as time-dependent DFT has been employed to optimize the geometry of the molecules, followed by computation of dipole moment (μ), static first hyperpolarizability (βtotal), and one- and two-photon absorption (TPA) strengths. The results reveal that dipole moment as well as total static first hyperpolarizability (βtotal) of the studied molecules is dominated by the respective components in the direction of charge transfer. The ratio of vector component of first hyperpolarizability (βvec) to βtotal also supports the unidirectional charge transfer in the studied systems. In molecule 3, which is a donor-acceptor-acceptor (D-A-A)-type system, the BODIPY moiety is found to play a major role in controlling the NLO response over the other acceptor group. Solvents are also found to play an important role in controlling the linear as well as NLO response of the studied systems. A significant increase in the first hyperpolarizability as well as TPA cross-section of the studied molecules is predicted due to an increase in the dielectric constant of the medium. The results presented are expected to provide a clue in tuning the NLO response of many ICT-based chromophores, especially those with D-A-A arrangements.