A fabric phase sorptive extractor (FPSE) is a sampling device where a flexible fabric is coated with at least one sol-gel derived film that includes at least two of a metal oxide portion, a siloxy portion, and an organic portion, where the gel has at least some amorphous portions. The FPSE is flexible such that it can be used in an extended form or draped over a solid surface to contact a gaseous, liquid, or solid environment and can be manipulated for placement in a container where the absorbed analyte can be removed from the FPSE for instrumental analysis. The FPSE can have specific functionalities that bind to specific analytes or can provide a general sorbent medium for extraction of a wide range of analytes, such that the sampling device can be employed for sampling analytes with biological, environmental, food, pharmaceutical, bio-analytical, clinical, forensic, toxicological, national security, public health, and/or safety implications.