The invention generally relates to systems and methods for analyzing an extracted sample using an immiscible extraction solvent. In certain embodiments, the invention provides a system for analyzing an analyte in a sample. The system includes an ionization probe and a mass spectrometer. The ionization probe includes a hollow body that optionally includes a distal tip. The hollow body is configured such that there is no substrate within the body and no electrode disposed on a surface of the body. An electrode is at least partially disposed within the hollow body.