Abstract: A novel lipophilic dirhenium complex fac-[{Re(CO)3(d19phen)}2(4,4′bipyridylacetylene)](OTf)2，(denoted as DRe(I))(d19phen=4,7dinonadecyl1,10phenanthroline and OTf=trifluoromethanesulfonate) was doped homogeneously in polystyrene(PS) and polymethyl methacrylate(PMMA) fibers by electrospinning method and the oxygen quenching fluorescence behavior was systematically investigated. The linear SternVolmer model, the Demas and Lehrer models were used to fit the obtained SternVolmer curves of the composite fibers. An oxygen sensor based on the DRe(I) composite fibers shows short response time, good reproducible signals, and linear SternVolmer plots attributed to the existence of the ligand containing long alkyl chain groups that makes DRe(I) become soluble in the polymers.