A system for solventless calibration of volatile or semi-volatile compounds and methods thereof. The system includes a fluid path having a first end configured to be operably coupled to a fluid source and a second end configured to be operably coupled to the analytical instrument. A solid sorbent is disposed along the fluid path and is configured to absorb an analyte. The flow of fluid along the fluid path from the first end to the second end causes absorbed analyte to be desorbed from the solid sorbent at a desired concentration to the instrument.