An Atmospheric Pressure Chemical Ionization (APCI) source interfaced to a mass spectrometer is configured with a corona discharge needle positioned inside the APCI inlet probe assembly. Liquid sample flowing into the APCI inlet probe is nebulized and vaporized prior to passing through the corona discharge region all contained in the APCI inlet probe assembly Ions produced in the corona discharge region are focused toward the APCI probe centerline to maximize ion transmission through the APCI probe exit. External electric fields penetrating into the APCI probe exit end opening providing additional centerline focusing of sample ions exiting the APCI probe. The APCI probe is configured to shield the electric field from the corona discharge region while allowing penetration of an external electric field to focus APCI generated ions into an orifice into vacuum for mass to charge analysis. Ions that exit the APCI probe are directed only by external electric fields and gas flow maximizing ion transmission into a mass to charge analyzer. The new APCI probe can be configured to operate as a stand alone APCI source inlet probe, as a reagent ion gun for ionizing samples introduced on solids or liquid sample probes or through gas inlets in a multiple function ion source or as the APCI portion of a combination Electrospray and APCI multiple function ion source. Sample ions and gas phase reagent ions are generated in the APCI probe from liquid or gas inlet species or mixtures of both.