A hybrid [4]arene-based co-crystal (H-TCNB) was developed to enable vapochromic separation of benzene (Bz) and toluene (Tol) from their mixtures with cyclohexane (Cy) and pyridine (Py). The co-crystal, formed by charge-transfer interaction between an electron-rich hybrid [4]arene (H) and an electron-deficient 1,2,4,5-tetracyanobenzene (TCNB), exhibits color changes from brown to yellow upon adsorption of Bz and Tol vapors, indicating structural transformation. In contrast, no structural or color changes occur when capturing Cy or Py vapors. The co-crystal effectively separates Bz from Bz/Cy mixtures and Tol from Tol/Py mixtures with 100% purity, and the process is visually monitorable. The selectivity is attributed to changes in charge-transfer interactions between H and TCNB upon adsorption of different vapors. The co-crystal can be reused without losing selectivity or performance. The material demonstrates high efficiency in hydrocarbon separation, with the ability to purify cyclohexane (Cy) from Bz/Cy mixtures and pyridine (Py) from Tol/Py mixtures. The vapochromic behavior is linked to solid-state structural transformations, and the co-crystal shows excellent recyclability. This study highlights the potential of hybrid [4]arene-based co-crystals for applications in petrochemical industry, environmental monitoring, and gas sensing.A hybrid [4]arene-based co-crystal (H-TCNB) was developed to enable vapochromic separation of benzene (Bz) and toluene (Tol) from their mixtures with cyclohexane (Cy) and pyridine (Py). The co-crystal, formed by charge-transfer interaction between an electron-rich hybrid [4]arene (H) and an electron-deficient 1,2,4,5-tetracyanobenzene (TCNB), exhibits color changes from brown to yellow upon adsorption of Bz and Tol vapors, indicating structural transformation. In contrast, no structural or color changes occur when capturing Cy or Py vapors. The co-crystal effectively separates Bz from Bz/Cy mixtures and Tol from Tol/Py mixtures with 100% purity, and the process is visually monitorable. The selectivity is attributed to changes in charge-transfer interactions between H and TCNB upon adsorption of different vapors. The co-crystal can be reused without losing selectivity or performance. The material demonstrates high efficiency in hydrocarbon separation, with the ability to purify cyclohexane (Cy) from Bz/Cy mixtures and pyridine (Py) from Tol/Py mixtures. The vapochromic behavior is linked to solid-state structural transformations, and the co-crystal shows excellent recyclability. This study highlights the potential of hybrid [4]arene-based co-crystals for applications in petrochemical industry, environmental monitoring, and gas sensing.