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Solid-phase microextraction (SPME) via on-fiber derivatization with O-(2,3,4,5,6-pentafluorobenzyl)-hydroxylamine (PFBHA) and gas chromatographic determination is considered a technique of choice in many analytical fields for formaldehyde (FA) monitoring. Vapor phase adsorption models of experimentally loaded PFBHA on porous divinylbenzene (DVB) SPME were investigated at 60°C, 35 cm s−1 of air velocity, in a 1-64 min range: with the fiber completely exposed, loaded PFBHA was about 276 μg. Among the models tested, i.e. heat transfer, pseudo-second-order (PSO), Elovich, intra-particle diffusion, extra-particle diffusion and Langmuir, PFBHA adsorption was best fit by the PSO model, showing agreement with experimental data (272 μg). The sampling rate of FA in our conditions, obtained with a permeation tube system, was in agreement with literature (17.4 and 18.3 mL min−1, respectively). Thus, an overall standardization of the sampling phase is presented, leaving the sampling time as the most crucial parameter to be set for future applications.