Structural and electronic properties of ternary clusters AlkTilNim, where k, l, and m are integers and k + l + m = 4, are investigated. These clusters are generated and studied by performing a two‐stage density functional theory (DFT) calculations using the Slater, Vosko, Wilks, and Nusair (SVWN) and Becke three‐parameter, Lee‐Yang‐Parr (B3LYP) functional exchange correlations. In the first stage, an unbiased global search algorithm coupled with a DFT code with a light exchange‐correlation and smaller basis sets are used to generate the lowest energy cluster structures. It is then followed by further optimization using another round of DFT calculation with heavy exchanged correlations and large basis set. Electronic properties of the structures obtained via the two‐stage procedure are then studied via DFT calculations. The results are illustrated in the form of ternary diagram. Our DFT calculations find that the stability of the cluster increases with the increase in the number of nickel atoms inside the clusters. Our findings provide new insight into the ternary metallic cluster through the structure, stability, chemical order, and electronic properties studies. Trimetallic nanoclusters are commonly studied for their interesting electronic and magnetic properties. However, there studies on this type of clusters with more than four atoms, conducted using unbiased initial configuration search, are rare and therefore timely. Here, one‐third of the uncovered AlkTilNim cluster structures are 2D planar, whereas the rest of the structures, but the highly nonsymmetrical Ti1Ni3, have trigonal pyramid‐like configuration. [ABSTRACT FROM AUTHOR]