Thorium is a natural alpha-emitting element occurring in various ores and has numerous industrial applications. Routine monitoring of potentially exposed workers is generally achieved through radiobioassay (urine and faeces). The procedures currently used for analysing actinides such as thorium in urine require lengthy chemical separation associated with long counting times by alpha-spectrometry due to low activity levels. Thus, their main drawback is that they are time-consuming, which limits the frequency and flexibility of individual monitoring. In this context, this study developed new radiochemical procedures based on the use of tertbutylcalixarenes bearing three carboxylic acid groups or three hydroxamic acid groups. These previous works demonstrated that these macrocyclic molecules immobilised on an inert solid support are excellent extractants for uranium, plutonium and americium. In this study, the authors investigated the thorium extraction by calixarene columns. Experiments were performed on synthetic solutions and on real urine samples. The influence of various parameters, such as the thorium solution pH and the column flow rate on thorium extraction, was studied. The results showed that both calixarenes are efficient to extract thorium. Thorium extraction is quantitative from pH=2 for synthetic solution and from pH=3 for real urine samples. This study has demonstrated that the column flow rate is a crucial parameter since its value must not be too high to achieve the steady-state complexation equilibrium. Finally, these results will be compared with those obtained for other actinides (U, Pu and Am) and the conditions of actinides' separation will be discussed.