Poly(arylether)s (PAEs) synthesized via nucleophilic aromatic substitution are well recognized as high performance engineering thermoplastics. This study highlights the recent developments in the PAE synthesis, which open new opportunities for material chemistry. Combining PAEs and COFs produces porous high-dimensional PAEs and/or extraordinarily stable COFs. Bio-PAEs introduce sustainability into high performance engineering materials, which may create a game-changing shift in the engineering plastic field. These developments represent a new direction of materials research and are worthy of effort.