Solid-phase microextraction (SPME) is a widely used sampling technique that has been proved to enable efficient extraction of a broad range of analytes. Generally, SPME achieves non-exhaustive extraction, and therefore the analyte mass transfer distribution in the sampled multiphase system should be considered while developing a calibration method. Here, a new method, aimed at quantifying the extracted analytes without the need to consider their mass distribution, is proposed. This method relies on the generation of mass response curves by loading a known analyte mass onto the absorbent phase of a SPME fiber, and then conducting analysis by the preferred technique. Precise and accurate deposition of analyte over the restricted dimension of a fiber is demonstrated for the first time by utilizing a drop-on-demand microdrop printer. This system enables direct, non-contact deposition of micron-sized drops containing negligible solvent volumes (<1 nL), on the center of the extraction phase of the fiber which enables immediate analysis. Printed fiber response curves were determined herein, with three model compounds of different volatility-2,4-dinitrotoluene (2,4-DNT), diphenylamine (DPA), and 1,3 diethyl-1,3-diphenylurea (ethyl centralite, EC), using two analytical techniques, gas chromatography-mass spectrometry (GC-MS) and ion mobility spectrometry (IMS). Quantification of the absolute amounts extracted by headspace SPME yielded comparable results between the two methods of analysis with only less than 10% variation for 2,4-DNT and EC and less than 30% for DPA. In comparison, quantification by the traditional liquid injection/spike response curves determined by each technique led to mass estimates that were significantly greater by hundreds of percent.