Sixty-one and forty-four compounds were identified from the volatile oils of the bast and fibers of Apocynum venetum by means of gas chromatography-mass spectrometry (GC-MS), respectively. The fatty acids, esters, ketones, aldehydes, alkanes, phenols, and miscellaneous compounds were found as the major components in both samples. Furthermore, both of volatile oils exhibited antibacterial properties against Staphylococcus aureus, Staphyloccus epidermidis, and Escherichia coli, whereas they showed weak inhibitory effects on Bacillus lentus and Candida albicans. These results confirmed the claim that A. venetum fibers have antibacterial properties and provide theoretical foundation to make better use of A. venetum fibers.