Recent developments in X-ray optics have allowed the development of a range of commercially available benchtop micro-XRF (μ-XRF) instruments that can produce X-ray spot sizes of 20-30 μm on the sample, allowing major and trace element analysis on a range of sample types and sizes with minimal sample preparation. Such instruments offer quantitative analysis using fundamental parameter based “standardless” quantification algorithms. The accuracy and precision of this quantitative analysis on geological materials, and application of micro-XRF to wider geological problems is assessed using a single benchtop micro-XRF instrument. Quantitative analysis of internal reference materials and international standards shows that such instruments can provide highly reproducible data but that, for many silicate materials, standardless quantification is not accurate. Accuracy can be improved, however, by using a simple type-calibration against a reference material of similar matrix and composition. Qualitative analysis with micro-XRF can simplify and streamline sample characterisation and processing for subsequent geochemical and isotopic analysis.