A study where the Hantzsch reaction is used to produce the chemical derivatization of formaldehyde in a supercritical medium is presented in this paper. Pressure, temperature and other parameters such as static and dynamic extraction time must be optimized to increase the yield of this kinetically controlled reaction. A 2(5-1) (resolution V) factorial design was used to study the significant parameters affecting the supercritical process in terms of resolution and sensitivity. A subsequent central composite design was employed to find the conditions of maximum response. Ultraviolet-visible spectrophotometry was used as the detection technique. The optimum conditions were used for the determination of formaldehyde in real finger-paints by means of the previous addition of known quantities of this analyte to the paint. Results were compared with those obtained with supercritical fluid extraction and subsequent chemical derivatization and an improvement of sensitivity as well as a reduction of time of analysis, solvent waste and reagents consumption were observed.