Liquid ionization chambers (LICs) offer an interesting tool in the field of small beam dosimetry, allowing better spatial resolution and reduced perturbation effects. However, some aspects remain to be addressed, such as the higher recombination and the effects from the materials of the detector. Our aim was to investigate these issues and their impact. The first step was the evaluation of the recombination effects. Measurements were performed at different SSDs to vary the dose per pulse, and the collection efficiency was obtained. The BEAMnrc code was then used to model the Cyberknife head. Finally, the liquid ionization chamber itself was modelled using the EGSnrc-based code Cavity allowing the evaluation of the influence of the volume and the chamber materials. The liquid ionization charge collection efficiency is approximately 0.98 at 1.5 mGy pulse(-1), the highest dose per pulse that we have measured. Its impact on the accuracy of output factors is less than half a per cent. The detector modelling showed a significant contribution from the graphite electrode, up to 6% for the 5 mm collimator. The dependence of the average electronic mass collision stopping power of iso-octane with beam collimation is negligible and thus has no influence on output factor measurements. Finally, the volume effect reaches 5% for the small 5 mm collimator and becomes much smaller (<0.5%) for diameters above 10 mm. LICs can effectively be used for small beam relative dosimetry as long as adequate correction factors are applied, especially for the electrode and volume effects.