Chemical warfare agents (CWAs) are toxic chemicals that have been used as disabling or lethal weapons in war, terrorist attacks, and assasinations. The Chemical Weapons Convention (CWC) has prohibited the use, development, production, and stockpiling of CWAs since its initiation in 1997, however, the threat of deployment still looms. Detection of trace CWAs post-deployment or post-remediation, in bulk matrices such as soil, often requires lengthy sample preparation steps or extensive chromatographic separation times. 3D-printed cone spray ionization (3D-PCSI), an ambient ionization mass spectrometric (MS) technique, provides a rapid, simple, and low-cost method for trace CWA analysis in soil matrices for both in-laboratory and in-field detection. Described here is the utilization of conductive 3D-printed cones to perform both rapid sampling and ionization for CWA simulants and hydrolysis products in eight solid matrices. The analysis of trace quantities of CWA simulants and hydrolysis products by 3D-PCSI-MS coupled to both a commercial benchtop system and a field-portable MS system is detailed. Empirical limits of detection (LOD) for CWA simulants on the benchtop MS ranged from 100 ppt to 750 ppb and were highly dependant on solid matrix composition, with the portable system yielding similar spectral data from alike matrices, albeit with lower sensitivity.