The efficiency of niobium(V) oxide as a sorbent phase for solid phase microextraction (SPME) was investigated. The thin glass-ceramic rod was coated with niobium(V) oxide using chemical vapor deposition and Nb(2)O(5) as a chemical precursor. Optimum conditions for the preparation and conditioning of the fibers are presented. The fibers were used for the extraction of a mixture of alcohols and a mixture of phenols from the headspace samples. The results obtained proved the suitability of niobium(V) oxide as a new SPME fiber. The calibration graphs for alcohols and phenols in a concentration range of 50-1000 microgl(-1) were linear (r>0.995) and the detection limits were below 0.8 microgl(-1) level. The repeatability for one fiber (n=6) under similar conditions was between 3 and 10.4%. The fiber-to-fiber reproducibility (n=6) was between 5 and 15%.