To elucidate the sources and chemical reaction pathways of organic vapors and particulate matter in the ambient atmosphere, real-time detection of both the gas and particle phase is needed. State-of-the-art techniques often suffer from thermal decomposition, ionization-induced fragmentation, high cut-off size of aerosols or low time resolution. In response to all these limitations, we developed a new technique that uses extractive electrospray ionization (EESI) for online gas and particle chemical speciation, namely the dual-phase extractive electrospray ionization time-of-flight mass spectrometer (Dual-Phase-EESI-TOF or Dual-EESI for short). The Dual-EESI was designed and optimized to measure gas- and particle-phase species with saturation vapor concentrations spanning more than 10 orders of magnitude with good linearity and a measurement cycle as fast as 3 min. The gas-phase selectivity of the Dual-EESI was compared with that of nitrate chemical ionization mass spectrometry. In addition, we performed organic aerosol uptake experiments to characterize the relative gas and particle response factors. In general, the Dual-EESI is more sensitive toward gas-phase analytes as compared to their particle-phase counterparts. The real-time measurement capability of the Dual-EESI for chemically speciated gas- and particle-phase measurements can provide new insights into aerosol sources or formation mechanisms, where gas-particle partitioning behavior can be determined after absolute parameterization of the gas / particle sensitivity.