The analytical techniques employed in industrial hygiene and their relationship to sampling systems are discussed. Measurement validity, references materials, validation and classification of sampling and analytical methods, and proficiency testing are examined. Personal sampling devices, air sampling parameters, and sample processing are evaluated. The analytical emphasis upon gas chromatography and atomic absorption spectrophotometry in the field of industrial hygiene is described. Newer techniques are discussed including inductively coupled plasma optical emission spectroscopy, electron spectroscopy for chemical analysis, X-ray fluorescence, ion chromatography, and derivative spectroscopy. Factors related to sampling, analysis, or the analyte itself that hinder the development of validated sampling and analytical methods are evaluated.