Vinyl chloride monomer (VCM) is widely used in the manufacture of polyvinylchloride (PVC) and is known to be a human carcinogen. This factor, coupled with the widespread use of PVC in such close human contact applications as food packaging, medical equipment, and potable water transport, makes the accuracy and reproducibility of the procedures concerned with trace VCM residue analysis of extreme importance. This work reports on some recent efforts to develop a capillary-based alternative to the established packed-column procedures through the use of multidimensional techniques of heartcutting, cryotrapping, and backflushing. Utilizing a commercial multidimensional conversion system, various problems associated with ultratrace level work are resolved in an effort to develop this capillary-based method. The problems addressed are common to many similar trace residue applications and the techniques presented here may prove useful to these situations as well.