Headspace (HS) extraction and preconcentration of volatiles by solid-phase microextraction (SPME) can improve the sensitivity and selectivity of ambient ionization-mass spectrometry approaches like direct analysis in real time (DART), but previous approaches to HS-SPME-DART-MS have been challenging to automate. This report describes the production of inexpensive, reusable solid-phase mesh-enhanced sorption from headspace (SPMESH) sheets by laser-etching mesh patterns into poly(dimethylsiloxane) (PDMS) sheets. Parallel headspace extraction of volatiles from multiple samples can be achieved by positioning the SPMESH sheets over multiwell plates and then attaching to a positioning stage for automated DART-MS quantitation. Using three representative odorants (3-isobutyl-2-methoxypyrazine, linalool, and methyl anthranilate), we achieved μg/L-ng/L detection limits with SPMESH-DART-MS, with the DART-MS step requiring only 17 min for 24 samples. Acceptable repeatability (24% or less day-to-day variation) and excellent recovery from a grape matrix (99-106%) could be achieved. Through use of a Teflon gasket and stainless steel spacers, cross-contamination between the headspaces of adjacent wells could be limited to roughly 1%. Optimum SPMESH extraction and desorption parameters were determined by response surface methodology. In summary, sheet-based SPMESH provides a sensitive, readily automated approach for coupling with DART-MS and achieving high-throughput trace-level volatile analyses.