The second-order nonlinear optical properties of Lindqvist-type organoimido polyoxometalates bearing donor and acceptor substituents are evaluated by employing density functional theory and time-dependent density functional theory using the omega B97X-D range-separated hybrid exchange-correlation functional to describe accurately the field-induced effects. The hyper-Rayleigh scattering responses, beta(HRS) (-2 omega; omega, omega), and the depolarization ratio are the targeted quantities. They are analyzed by resorting to the two-state model, which reduces the full summation-over-state expression to a single diagonal term and relates the response to a few spectroscopic quantities. The validity of this model is demonstrated by its ability to reproduce the beta(HRS) variations as a function of the nature of the ligand, owing to the dominant 1D character of these organic-inorganic hybrids. The calculated values are in good agreement with the recent experimental work of Al-Yasari et al. (Inorg. Chem. 2017, 56, 10181-10194), which demonstrates that the hexamolybdate moiety plays the role of an electron acceptor group. On the contrary, they contradict previous studies, which attributed an electron donor character to the polyoxometalate moiety. Calculations highlight that (i) combining the hexamolybdate unit with an organic ligand bearing a strong donor substituent leads to an enhanced first hyperpolarizability, associated with a dominant low-energy excited state, characterized by a large excitation-induced electron transfer from the donating ligand to the hexamolybdate, therefore coupling the polyoxometalate (POM) and its substituted ligand; (ii) in the case of weaker donor substituents, the hexamolybdate still behaves as an electron acceptor, but the first hyperpolarizability is smaller and the coupling has a reduced spatial extension; and, on the contrary, (iii) in the presence of an acceptor substituent, there is a competition between the hexamolybdate and this group so that the first hyperpolarizability becomes very small. The whole set of results demonstrates that polyoxometalate moieties are good candidates to achieve large second-order nonlinear optical (NLO) responses while keeping a rather large transparency window and also that there remains space to improve their integration into NLO efficient organic-inorganic hybrids.