Formaldehyde was quantitatively analyzed by on fiber derivatization in biological tissues and fluid. It was sampled by derivatization with α-(2,3,4,5,6-pentafluoro benzyl-hydroxyamine hydrochloride(PFBHA) adsorbed onto polydimethylsiloxane/divinylbenzene (PDMS/DVB) solid phase microextraction fiber. We determined the optimal conditions of formaldehyde analysis with derivatization and adsorption by GC/MS. At first, PFBHA was loaded onto the fiber by headspace method in an aqueous PFBHA solution at room temperature for 5 min. One milliliter or gram of standards or biological tissues was placed in a 10 mL headspace vial and was heated for 20 min at 70 ℃. The PFBHA-loaded SPME fiber was introduced into the headspace for 40 min with agitation and then analyzed. The standard calibration curve was linear between 0 ~ 10.0 μg/mL of formaldehyde concentration with a correlation coefficient of 0.99. In the actual case of finding the human remains in Hyehaw-dong, formaldehyde was detected in the range of 0.46 ~ 4.76 μg/g in various tissues. Therefore, it suggested that these human remains were specimens of medical center of university.