Assessing pollutant concentrations can be hampered by the complex matrices found in the dairy supply/processing chain. Matrix effects were examined using solid‐phase microextraction (SPME) used to sample haloacetic acid methyl esters (HAAMe) and para‐cresol. In general, HAAMe were more difficult to detect with a polydimethylsiloxane fibre than with carboxen–polydimethylsiloxane fibre. Headspace sampling generally provided better detection of HAAMe than direct immersion with the reverse true for para‐cresol. For para‐cresol, equivalent ratios up to 18.8 were detected. Other compounds detected included sulphides, VOC's, phenols and indoles. For milk samples, most compounds collected by SPME were found using direct immersion.