A novel attempt in exploring the isomer separation capability of Hydroxyl Double Salts (HDSs), layered nanohybrids is conducted via competitive intercalation. Typical Zn HDS and new formulated Ni/Zn type HDSs demonstrated unique but reverse intercalation preference towards an equal mole isomeric mixture solution of 1-naphthoate and 2-naphthoate anions solution. The research successfully exemplified the feasibility of controlling the intercalation chemistry of HDSs by formulating their metal composition.