Metal–organic frameworks (MOFs) are excellent porous materials with nanoscale cavities and high surface areas, which make them promising as novel adsorbents in solid‐phase extraction (SPE). In this article we report a new application of the chiral MOF [Zn2(D‐Cam)2(4,4′‐bpy)]n in SPE used for the measurement of the enantiomeric excess (ee) of (±)‐1,1′‐bi‐2‐naphthol. Several important experimental parameters that may influence the extraction efficiency were investigated and optimized. Under the optimum conditions, a good linearity (R2 > 0.999) was found between the ee value and the reciprocal of the peak areas. When compared with the actual ee measured using chiral HPLC, the SPE‐based assay also showed good accuracy and precision. The results showed that SPE based on chiral MOFs as adsorbents is a simple and effective method for the determination of the ee values of chiral compounds.