The monitoring of ambient doses at work places around accelerators is a challenging task due the complexity of the mixed stray radiation fields encountered. At CERN, mainly Centronics IG5 high-pressure ionisation chambers are used to monitor radiation exposure in mixed fields. The monitors are calibrated in the operational quantity ambient dose equivalent H*(10) using standard, source-generated photon- and neutron fields. However, the relationship between ionisation chamber reading and ambient dose equivalent in a mixed high-energy radiation field can only be assessed if the spectral response to every component and the field composition is known. Therefore, comprehensive studies were performed at the CERN-EU high-energy reference field facility where the spectral fluence for each particle type has been assessed with Monte Carlo simulations. Moreover, studies have been performed in an accessible controlled radiation area in the vicinity of a beam loss point of CERN's proton synchrotron. The comparison of measurements and calculations has shown reasonable agreement for most exposure conditions. The results indicate that conventionally calibrated ionisation chambers can give satisfactory response in terms of ambient dose equivalent in stray radiation fields at high-energy accelerators in many cases. These studies are one step towards establishing a method of 'field calibration' of radiation protection instruments in which Monte Carlo simulations will be used to establish a correct correlation between the response of specific detectors to a given high-energy radiation field.