Identification of wildlife species from indirect evidence can be an important part of wildlife management, and conventional methods can be expensive or have high error rates. We used chemical characterization of the volatile organic constituents (VOCs) in scat as a method to identify 5 species of North American canids from multiple individuals. We sampled vapors of scats in the headspace over a sample using solid-phase microextraction and determined VOC content using gas chromatography with a flame ionization detector. We used linear discriminant analysis to develop models for differentiating species with bootstrapping to estimate accuracy. Our method correctly classified 82.4% (bootstrapped 95% CI = 68.8–93.8%) of scat samples. Red fox (Vulpes vulpes) scat was most frequently misclassified (25.0% of scats misclassified); red fox was also the most common destination for misclassified samples. Our findings are the first reported identification of animal species using VOCs in vapor emissions from scat and suggest that identification of wildlife species may be plausible through chemical characterization of vapor emissions of scat.