<p>In this study, the coordination pathways and decomposition behavior of azo-containing dicyano compounds within Fe(acac)₃/Al^<i>i</i>Bu₃/donor ternary catalyst systems were systematically investigated <i>via in situ</i> Raman spectroscopy. Additionally, the modulating effect of conjugated moieties on the coordination interaction between cyanide groups and Fe ions was examined in detail. Experimental results demonstrate that isoprene polymerization catalyzed by azodicyanide mediated Fe-based catalytic systems proceeds <i>via</i> a coordination polymerization mechanism. Notably, the azo group does not directly participate in the coordination process; instead, it exerts a regulatory influence on the coordination capacity of the cyano group. Although thermal decomposition of the azo group occurs at elevated temperatures, it fails to initiate free radical polymerization of the isoprene monomer. Conjugated moieties including azo, vinyl, and benzene rings exert distinct impacts on the cyanide group. As electron-donating species, their Raman spectral characteristics reflect varying influences on cyanide coordination behavior. Density functional theory (DFT) calculations demonstrate that AIBN with azo groups as the conjugated moiety exhibits the most negative Gibbs free energy (Δ<i>G</i>°=−222.71 kcal·mol⁻¹) for the coordination reaction with Fe²⁺, indicating that the cyano groups in the azo-containing compound possess the strongest coordination capability with Fe²⁺. The coordination effects of conjugated groups on the cyanide center follow the sequence: azo &gt; carbon-carbon double bond &gt; benzene ring, where azo groups show the most significant coordination enhancement. These theoretical findings are consistent with the observed polymerization activity, suggesting that rational design of electron donors can be guided by theoretical calculations.</p>