The concept of ambient desorption-optical emission spectroscopy (AD-OES) is demonstrated using a liquid sampling-atmospheric pressure glow discharge (LS-APGD) microplasma as the desorption/excitation source. The LS-APGD has previously been employed for elemental analysis of solution samples and particulates introduced via laser ablation in both the optical emission and mass spectrometries (OES, MS) modes. In addition, the device has been shown to be effective for the analysis of elemental and molecular species operating in an ambient desorption/ionization mass spectrometry (ADI-MS) mode. Proof-of-concept is presented here in the use of the LS-APGD to volatilize three very diverse sample forms (metallic thin films, dry solution residues, and bulk materials), with the liberated material excited within the microplasma and detected via OES, i.e., AD-OES. While the demonstration is principally qualitative at this point, it is believed that the basic approach may find application across a broad spectrum of analytical challenges requiring elemental analysis, including metals, soils, and volume-limited solutions, analogous to what has been seen in the development of the field of ADI-MS for molecular species determinations.