Hexanal and heptanal are two promising aldehydes that have been found in biological samples of lung cancer patients. In general, aldehydes can be detected in trace level as low as part per billion or part per trillion levels. Since reliable technique is needed to detect the analyte of interest especially in complex matrices, a new hybrid silica-based material as the adsorbent of hollow fiber-solid phase microextraction (HF-SPME) was synthesized. In the present work, the solgel hybrid material was held in the pores of HF by in situ gelation and was used to extract the two test aldehydes using direct immersion sampling mode. Several solgel parameters affecting the extraction performance of the in-house sol-gel hybrid material were optimized. The extraction efficiencies of the new silica-based hybrid material for the target aldehydes were based on peak area response obtained from gas chromatography-flame ionization detector. The best extraction efficiencies of hexanal and heptanal were obtained using a mol ratio of 1:4 for the two precursors used, 6 mmol water, 6 mmol methanol and 2.5 mmol trifluoroacetic acid for in situ gelation HF-SPME. The new in situ sol-gel silicabased adsorbent material exhibits high potential for HF-SPME of hexanal and heptanal