Theoretical examinations of reactivity for the formal [2 + 2] cycloaddition of Me-C≡C-Ph to Group-6(G6)≡Group-14(G14) triple-bonded organometallic complexes have been carried out using the M06-2X-D3/def2-TZVP level of theory. Our theoretical findings suggest that Me-C≡C-Ph can undergo adduct formation with all G6≡Si complexes, resulting in the generation of four-membered ring structures. However, among the W≡Group-14 complex reactants, only W≡Si-based, W≡Ge-based, and W≡Sn-based organometallic molecules are capable of undergoing a [2 + 2] cycloaddition reaction with Me-C≡C-Ph. Based on energy decomposition analysis, our theoretical investigations demonstrate that the bonding mechanism in such [2 + 2] cycloaddition reactions involves the creation of two dative bonds between singlet fragments (the donor-acceptor model), as opposed to two electron-sharing bonds between triplet fragments. In addition, the examinations based on the activation strain model indicate that the activation barrier of the [2 + 2] cycloaddition reaction is predominantly governed by the geometric deformation energy of the two reactants (G6≡G14-Rea and Me-C≡C-Ph). Our research using the M06-2X method shows that the barrier heights of [2 + 2] cycloaddition reactions between Me-C≡C-Ph and G6≡Si-Rea are dependent on the geometric changes occurring in both fragments during the transition states, consistent with Hammond's postulate.