Trianglimine (TI) and trianglamine (TA) macrocycles offer an efficient adsorptive molecular sieving strategy to separate toluene (Tol) from an equimolar mixture of Tol and methylcyclohexane (MCH) with 98.3% and 96.4% selectivity, respectively. Selective separation is achieved through the intrinsic cavity or extrinsic channel within the crystalline molecular absorbents, driven by C–H⋯π and π⋯π interactions. Moreover, TI and TA exhibit exceptional recyclability, highlighting their potential for sustainable chemical separation processes.