Headspace analysis is used widely and relies on volatilization of analytes into the headspace above the matrix. We detail the dramatic influence that added solvent can have on headspace analysis of phenols, without the requirement for specialized headspace vials. The use of water-immiscible solvents is key and leads to a 1鈥? orders of magnitude enhancement in the volatilization of these analytes and shorter fiber exposure times than are otherwise required.