Four nickel carbonate-bearing minerals from Australia have been investigated to study the effect of Ni for Mg substitution. The spectra of nullaginite, zaratite, widgiemoolthalite and takovite show three main features in the range of 26,720–25,855 cm⁻¹ (ν₁-band), 15,230–14,740 cm⁻¹ (ν₂-band) and 9,200–9,145 cm⁻¹ (ν₃-band) which are characteristic of divalent nickel in six-fold coordination. The Crystal Field Stabilization Energy (CFSE) of Ni²⁺ in the four carbonates is calculated from the observed ³A_2g(³F) → ³T_2g(³F) transition. CFSE is dependent on mineralogy, crystallinity and chemical composition (Al/Mg-content). The splitting of the ν₁- and ν₃-bands and non-Gaussian shape of ν₃-band in the minerals are the effects of Ni-site distortion from regular octahedral. The effect of structural cation substitutions (Mg²⁺, Ni²⁺, Fe²⁺ and trivalent cations, Al³⁺, Fe³⁺) in the carbonate minerals is noticed on band shifts. Thus, electronic bands in the UV–Vis–NIR spectra and the overtones and combination bands of OH and carbonate ion in NIR show shifts to higher wavenumbers, particularly for widgiemoolthalite and takovite.