This study explores the development of a macrocycle co-crystal based on hybrid[4]arene and 1,2,4,5-tetracyanobenzene (TCNB) for vapor-induced structural transformation and selective adsorption of hydrocarbons. The co-crystal, named H-TCNB, changes color from brown to yellow upon capturing benzene (Bz) and toluene (Tol) vapors, while remaining unchanged when exposed to cyclohexane (Cy) and pyridine (Py). H-TCNB effectively separates Bz from a Bz/Cy mixture and Tol from a Tol/Py mixture with 100% purity. The selectivity is attributed to the charge-transfer interactions between H-TCNB and the vapors, which alter the crystal structure. H-TCNB can be reused without losing its selectivity and performance, making it a promising material for hydrocarbon separation. The study also highlights the potential of hybrid[4]arene-based co-crystals in various applications, including environmental monitoring and gas sensing.This study explores the development of a macrocycle co-crystal based on hybrid[4]arene and 1,2,4,5-tetracyanobenzene (TCNB) for vapor-induced structural transformation and selective adsorption of hydrocarbons. The co-crystal, named H-TCNB, changes color from brown to yellow upon capturing benzene (Bz) and toluene (Tol) vapors, while remaining unchanged when exposed to cyclohexane (Cy) and pyridine (Py). H-TCNB effectively separates Bz from a Bz/Cy mixture and Tol from a Tol/Py mixture with 100% purity. The selectivity is attributed to the charge-transfer interactions between H-TCNB and the vapors, which alter the crystal structure. H-TCNB can be reused without losing its selectivity and performance, making it a promising material for hydrocarbon separation. The study also highlights the potential of hybrid[4]arene-based co-crystals in various applications, including environmental monitoring and gas sensing.