Moreover, pillar[n]arene-type macrocycles are receiving increasing attentions for practical applications in chemical industry. Recently, Huang, Cooper and co-workers have elegantly demonstrated various kinds of isomeric separations with pillar [n]arenes for what they called "nonporous adaptive crystals (NAC)" strategy. However, one crucial factor is holding this promising class of porous materials back. That is, the building blocks (benzene derivatives) for these materials are all petroleum-based chemicals. This would create an environmental burden for their potential mass production, which discount their overall practical aspect. Our work is expected to inspire more environmentally friendly pathway to convert biomass waste-derived building blocks (5 is converted from furfural) into unique petroleum-based functional materials. ASSOCIATED CONTENT