Recently, a new sulfide cluster fullerene, Sc₂S@C_s (10528)-C₇₂ containing two pairs of fused pentagons has been isolated and characterized (Chen et al., J. Am. Chem. Soc., 2012, 134, 7851). Inspired by this investigation, we propose a question: what properties will be influenced by the interaction between the encapsulated V-shaped polar molecule and C₇₂? To answer this question, four encapsulated metallic fullerenes (EMFs) M₂N@C₇₂ (M = Sc or Y, N = S or O) along with pristine C_s-C₇₂ (10528) were investigated by quantum chemistry methods. The results show that the E_gap (3.01–3.14 eV) of M₂N@C₇₂ are significantly greater than that of pristine C_s-C₇₂ (10528) (2.34 eV). This indicates that the stabilities of these EMFs increase by encapsulating the V-shaped polar molecule into the fullerene. Furthermore, the natural bond orbital (NBO) charge analysis indicates electron transfer from M₂N to C₇₂ cage, which plays a crucial role in enhancing first hyperpolarizability (β_tot). The β_tot follows the order of 1174 au (Y₂O@C₇₂) ≈ 1179 au (Sc₂O@C₇₂) > 886 au (Y₂S@C₇₂) ≈ 864 au (Sc₂S@C₇₂) > 355 au (C₇₂). This indicates that the β_tot of M₂N@C₇₂ is more remarkable than that of pristine C_s-C₇₂ (10528) due to the induction effect of the encapsulated molecule. Compared with sulfide cluster fullerenes (Y₂S@C₇₂ and Sc₂S@C₇₂), oxide cluster fullerenes (Sc₂O@C₇₂ and Y₂O@C₇₂) show much larger β_tot due to the small ionic radius and the large electronegativity of oxygen. In contrast, the metal element (scandium and yttrium) has a slight influence on the β_tot. Thus, oxide cluster fullerenes are candidates to become promising nonlinear optical materials with higher performance.