An efficient synthetic route to an A1/A2-difunctionalized pillar[5]arene containing resolvable planar chirality has been developed and the arene employed as a strut in the synthesis of P5A-MOE-1, which has been demonstrated by X-ray powder diffraction analysis-supported by modeling-to be isoreticular with MOF-5. This metal-organic framework has an active domain that expresses good and selective uptake of neutral and positively charged electron-poor aromatic guests, which effect color changes of the cubic crystals from faint yellow to deep orange, arising from charge transfer between the guests and active domain of P5A-MOE-1.