A novel lipophilic dirhenium complex fac-[{Re(CO)3(d19phen)}2(4,4′bipyridylacetylene)](OTf)2,(denoted as DRe(I))(d19phen=4,7dinonadecyl1,10phenanthroline and OTf=trifluoromethanesulfonate) 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 SternVolmer model, the Demas and Lehrer models were used to fit the obtained SternVolmer curves of the composite fibers. An oxygen sensor based on the DRe(I) composite fibers shows short response time, good reproducible signals, and linear SternVolmer plots attributed to the existence of the ligand containing long alkyl chain groups that makes DRe(I) become soluble in the polymers.