Systems and methods for atmospheric pressure chemical ionization are provided herein. In various aspects, the APCI apparatus, systems, and methods can provide an asymmetric sample spray into a vaporization chamber asymmetrically (e.g., off axis from the longitudinal axis of the vaporization chamber) so as to increase the interaction of the molecules in the sample spray with the vaporization chamber's sidewalls (and expose more of the molecules to the heat generated thereby), which can thereby result in improved consistency and/or efficiency of ion formation, and/or increased sensitivity relative to conventional APCI techniques.