This study explores the simultaneous presence of two metal ions of Nickel (Ni) and Copper (Cu) on the formation of a metal selenide (Ni-doped CuSe) in an alkaline environment. The impact of Ni ions on creating the second optical transitions is investigated. Different concentrations amounts of Ni ions (0.01, 0.02, and 0.03 mol) are utilized to produce Ni-doped CuSe semiconductor thin films through a chemical solution deposition method with deposition times varying from 3 to 6 h. Absorbance spectra are employed to determine the band-gap, while Field Emission Scanning Electron Microscopy is utilized for morphological analysis. Structural and elemental analyses are conducted using X-ray Diffraction and Energy Dispersive X-ray Spectroscopy techniques. Additionally, a relatively innovative approach for determining the optical transitions, termed the Derivation Ineffective Thickness Method (DITM), is employed. DITM eliminates the need for thin film thickness and assumptions about the type of transition (direct or indirect) for band-gap calculation. Moreover, a comparison is made between the band-gap obtained from the Tauc model and the transitions obtained by DITM method. Furthermore, it is demonstrated that the optical transitions exhibit two distinct band-gaps associated with nickel selenide (NiSe) as second transition and copper selenide (CuSe) as fundamental transition. The presence of Ni is also found to enhance crystal quality. The study also briefly explores the improved photocatalytic properties of CuSe in the presence of Ni.