ABSTRACT In this paper we describe the use of electrospray-assisted pyrolysis ionization/mass spectrometry (ESA-Py/MS) to selectively ionize trace polar compounds that coexist with large amounts of nonpolar hydrocarbons in synthetic polymer, crude oil, amber, humic substances, and rubber. Samples of different origins are distinguished rapidly by their ESA-Py mass spectra without prior separation or chemical pretreatment. During ESA-Py analysis, the samples in their solid or liquid states were pyrolyzed at 590 ¢XC using a commercial Curie-point pyrolytical probe; the gaseous pyrolysates were transferred into a glass reaction cell; the polar compounds (M) in the pyrolysates were then ionized in the form of protonated molecules (MH+), through their reactions with the charged species in the ESI plum. Although the major components of the pyrolysates are nonpolar hydrocarbons, their lack of functional groups that can receive a proton in the ESA-Py source results in no hydrocarbon ion signals being produced; thus, the ions detected in ESA-Py mass spectra all result from trace polar component in the pyrolysates.