The analysis of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, polychlorinated biphenyls, and other related dioxin-like compounds requires complex sample preparation and analytical procedures using highly sensitive and selective state-of-the-art instrumentation to meet very stringent data quality objectives. The analytical procedures (extraction, sample preparation), instrumentation (chromatographic separation and detection by mass spectrometry), and screening techniques for the determination of dioxins, furans, dioxin-like polychlorinated biphenyls, and related compounds with a focus on new approaches and alternate techniques to standard regulatory methods are reviewed.