Flexible conductive fibers were fabricated by in-situ chemical polymerization of pyrrole monomers on the surface of polyurethane (PU) fibers. Compact polypyrrole (PPy) surface layer were observed, and moreover, high structural stability of the composite fibers can be obtained due to interpenetrating interface formation and strong interaction between PPy layers and PU matrix. More importantly, the composite fibers exhibited high sensitivity with relative fast response and recovery time, and good reproducibility for chloroform vapor detection.