We detail the development and characterization of a GC/QLT-Orbitrap hybrid mass spectrometer capable of high resolution (up to 100,000 at m/z 400) and sub-parts-per-million mass accuracy GC/MS. A high-duty cycle, innovative scan type, the nested scan, was implemented to synchronize the Orbitrap acquisition rate and the time scale of gas chromatography (up to 6.5 Hz at resolution 7500). We benchmark this instrument's key figures of merit, including resolution, mass accuracy, linear dynamic range, and spectral accuracy, and demonstrate its performance for two challenging applications: the determination of polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) in environmental samples and the profiling of primary metabolites in Arabidopsis thaliana extracts.