Saliva is progressively becoming a useful alternative to urine and blood to assess human exposure to toxics in biomonitoring campaigns, because of its easy and stress-free collection by unskilled personnel. This evaluation is highly challenging owing to the large number of compounds and individuals involved. In this article, we propose a new strategy to simplify sample treatment in the human biomonitoring of toxics in saliva. It is based on the in situ formation of supramolecular solvents (SUPRASs) in the sample. For this purpose, SUPRASs were produced in colloidal suspensions of aggregates of hexanol in THF under the addition of saliva, which played the dual role of inductor of the self-assembly process leading to SUPRAS formation and the sample to be analysed. The SUPRAS formation region was delimited from the phase diagram constructed for the ternary mixture saliva/hexanol/THF. An equation was derived for predicting the volume of SUPRASs produced as a function of the proportion of their components. The new strategy was explored for simplifying sample treatment in the biomonitoring of thirteen free bisphenol analogues and derivatives by liquid chromatography tandem mass spectrometry. Absolute recoveries for bisphenols were in the range 95-105.6%, the method was interference free (signal suppression/enhancement was between 93 and 106%), and the repeatability and within laboratory reproducibility were in the intervals 0.6-10% and 2-16%, respectively. The proposed method was fully validated and it was applied to the determination of the target bisphenols in saliva from 13 volunteers. Free bisphenol A was found in all samples (0.057-0.8 μg L), and bisphenol F, bisphenol S and bisphenol AF were found with a frequency of detection of 46%, 62% and 8%, respectively. So, saliva can be a suitable biological sample for studying human exposure to bisphenols. To the best of our knowledge, this is the first report dealing with the use of saliva for biomonitoring human exposure to bisphenols.