Modified technique in calculating the dipole moments for square pyramidal complexes has been developed and then the dipole moments for bisacetylacetonato(oxo)vanadium(Ⅳ) complexes are calculated, adopting this approach. The calculated dipole moments for bisacetylacetonato(oxo)vanadium(Ⅳ) in benzene and bisacetylacetonato(oxo)vanadium in dioxane solutions are in agreement with the observed values. The calculated dipole moments of bisacetylacetonato(oxo)vanadium(Ⅳ) in dioxane solution is slightly higher than that of bisacetylacetonato(oxo)vanadium(Ⅳ) in benzene. Such a result may suggest that bisacetylacetonato(oxo)vanadium(Ⅳ) interact with dioxane molecule to form bisacetylacetonato(oxo)vanadium(Ⅳ)-dioxane adduct. This calculated dipole moments are also in agreement with the experimental results.