<p>Laser micropyrolysis gas chromatography-mass spectrometry enables researchers to selectively obtain chemical information about the organic matter in specific parts of a variety of specimens, such as coals and fossils, in order to elucidate chemical composition. This paper briefly reviews the history of this type of pyrolysis and examines whether the technique can be used to isolate and recover biogeochemical signatures directly from the mineralised organophosphatic sclerites of Cambrian tommotiids-a group of enigmatic lophotrochozoans-and potentially related organophosphatic brachiopods. We analysed specimens of two tommotiids (<i>Micrina etheridgei</i> and <i>Dailyatia</i> sp.) and the paterinate brachiopod <i>Askepasma toddense</i> from the lower Cambrian of South Australia. Pyrolysate hydrocarbons from the sclerites of these species were detected and compared. Results indicate that <i>A. toddense</i> is more chemically complex than either of the two tommotiid taxa, but that <i>M. etheridgei</i> is compositionally more similar to <i>A. toddense</i>. Importantly, this study has demonstrated that laser micropyrolysis gas chromatography-mass spectrometry of Cambrian organophosphatic small shelly fossils yields detectable pyrolysates that have geochemical significance. It will be analytically possible and useful in the future to apply this technique to a larger sample set to elucidate deep time biogeochemical homologies, and to test intra-shell heterogeneity.</p>