This investigation focuses on the solid-state synthesis and a detailed structural and phase analytical investigation of the Co ???? Ni 3−???? Ga 4 series along a constant Ga compositional line within Co⎼Ni⎼Ga phase space. Combined analysis of single crystal X-ray diffraction and neutron powder diffraction of Co ???? Ni 3−???? Ga 4 , 𝑥 = 1.5 reveals a random distribution of Co and Ni over a single Wyckoff site, which contrasts with previous report suggesting atomic ordering. Phase analyses via X-ray powder diffraction indicates a vacancy order-disorder transition as the Co concentration increases beyond a critical limit. DFT calculation predicted a semi-metallic and nonmagnetic ground state, supported by the absence of magnetic peaks or intensity enhancement at 10 K neutron data compared to 300 K. Interestingly “Peierls-like” distortions are observed within the Ga substructure in the vacancy-ordered phase, whereas such distortions are absent in the vacancy-disordered phase. These distortions result in periodic charge localization and exhibit subtle alterations between room temperature and 180 K. Magnetic measurements further reveal cluster spin-glass behavior with a high coercivity. The non-trivial spin dynamics, coupled with large coercivity, makes this phase a compelling candidate for multifunctional applications.