Two soluble poly(aryl ether)s were prepared conveniently from bis(4-hydroxy-3,5-dimethylphenyl)naphthylmethane (1) and two activated dihalide monomers including 4,4′-difluorobenzophenone and bis(4-chlorophenyl)sulfone by an aromatic nucleophilic substitution. The bulky naphthyl and tetramethyl pendant groups in the polymer backbone could decrease the packing density and intermolecular interaction of macromolecular chain and make these poly(aryl ether)s show a good solubility. They all could be dissolved in CHCl3, CH2Cl2 and tetrahydrofuran at room temperature with a dissolvability of more than 10 wt%. Furthermore, the poly(aryl ether)s could be electrospun into microfiber (10–15 μm) with nanopores (200–350 nm). The morphologies of these fibers were characterized by scanning electron microscopy. The porous morphology on the fiber surface was also investigated using scanning probe microscope.