The evaluation of a novel prototype instrument designed for on-site determinations of VOC mixtures found in indoor working environments is described. The instrument contains a miniature multi-stage preconcentrator, a dual-column separation module with pressure-tunable retention capabilities, and an integrated array of three polymer-coated surface acoustic wave sensors. It was challenged with dynamic test-atmospheres of a set of 15 common indoor air contaminants at parts-per-billion concentrations within a stainless-steel chamber under a range of conditions. Vapours were reliably identified at a known level of confidence by combining column retention times with sensor-array response patterns and applying a multivariate statistical test of pattern fidelity for the chromatographically resolved vapours. Estimates of vapour concentrations fell within 7% on average of those determined by EPA Method TO-17, and limits of detection ranged from 0.2 to 28 ppb at 25 °C for 1 L samples collected and analyzed in <12 min. No significant humidity effects were observed (0–90% RH). Increasing the chamber temperature from 25 to 30 °C reduced the retention times of the more volatile analytes which, in turn, demanded alterations in the scheduling of column-junction-point pressure (flow) modulations performed during the analysis. Reductions in sensor sensitivities with increasing temperature were predictable and similar among the sensors in the array such that most response patterns were not altered significantly. Short-term fluctuations in concentration were accurately tracked by the instrument. Results indicate that this type of instrument could provide routine, semi-autonomous, near-real-time, multi-vapour monitoring in support of efforts to assess air quality in office environments.