The adsorption capacity of synthetic NaX zeolite for Pb²⁺, Cd²⁺, Cu²⁺ and Zn²⁺ in single and multi-component systems were investigated. The effects of electronegativity and hydration energy on the selective adsorption, as well as potential selective adsorption mechanism of the NaX zeolite for Pb²⁺, Cd²⁺, Cu²⁺ and Zn²⁺ were also discussed. The maximum adsorption capacity order of the heavy metals in the single system was Pb²⁺ > Cd²⁺ > Cu²⁺ > Zn²⁺, and this could be related to their hydration energy and electronegativity. The values of the separation factors (α) and affinity constant (K_EL) in different binary systems indicated that Pb²⁺ was preferentially adsorbed, and Zn²⁺ presented the lowest affinity for NaX zeolite. The selective adsorption capacities of the metals were in the order, Pb²⁺ > Cd²⁺ ≈ Cu²⁺ > Zn²⁺. The trend for the selective adsorption of NaX zeolite in ternary and quaternary systems was consistent with that in the binary systems. Pb²⁺ and Cu²⁺ reduced the stability of the Si-O-Al bonds and the double six-membered rings in the NaX framework, due to the high electronegativity of Pb²⁺ and Cu²⁺ than that of Al³⁺. The selective adsorption mechanism of NaX zeolite for the high electronegative metal ions could mainly result from the negatively charged O in the Si-O-Al structure of the NaX zeolite, hence heavy metal ions with high electronegativity display a strong affinity for the electron cloud of the oxygen atoms in the Si-O-Al. This study could evaluate the application and efficiency of zeolite in separating and recovering certain metal ions from industrial wastewater.