Chloroform is a volatile organic solvent and a contaminant that is slightly soluble in water, making the reversible separation of chloroform from water a critical and challenging task within the chemical and environmental industries. In this study, we present a newly developed coordination framework, [Zn(4-pmntd)(opa)] [4-pmntd, N,N′-bis(4pyridylmethyl)naphthalene diimide; opa, o-phthalic acid], which demonstrates a high adsorption capacity for chloroform (2.5 mmol/g) and an excellent ability to separate chloroform from water. The effectiveness of chloroform extraction by Zn(4-pmntd)(opa) was confirmed through vapor sorption, grand canonical Monte Carlo simulation, and 1 H nuclear magnetic resonance spectroscopy. The porous framework was also utilized to create a filtration film using natural rubber, which successfully separated chloroform from water with a minimum test concentration of approximately 1 × 10 −6 mol/L and a chloroform purity of 99.2%. [Zn(4-pmntd)(opa)] therefore has significant potential for lowenergy separation and recycling of chloroform from water under ambient conditions.