Disclosed are polyarylene ether sulfides and polyarylene ether sulfones for optical device and a method for preparing the same. Polyarylene ether sulfides containing fluorine and polyarylene ether sulfones containing fluorine are synthesized through polycondensation of pentafluorophenyl sulfide and pentafluorophenyl sulfone monomer with dihydroxy monomer. In addition, by attaching ethynyl phenol and phenylethynylphenol to terminals of the high molecular weight polymer, solvent resistance of the polymer is increased. Thus, the high molecular weight polymers prepared by very simplified process have low light loss, excellent resistance for heat, solvent and water, and so can be used to manufacture inactive optical waveguide devices.