Airflow-enhanced evaporation is investigated as a method for rapid chemical preconcentration on a thin porous substrate. The mechanism is described by combining 1D models of capillary rise, chromatography, and pervaporation concentration. It is shown that the effective length of the column can be shorter than its actual length, allowing concentrate to be held at a stagnation point and then released for separation, and that the Péclet number, which determines the concentration performance, is determined only by the substrate properties. The differential equations are solved dynamically, and it is shown that faster concentration can be achieved during capillary filling. Experiments are carried out using chromatography paper in a ducted airflow, and concentration is quantified by optical imaging of water-soluble food dyes. Good agreement with the model is obtained, and concentration factors of ≈100 are achieved in 10 min using Brilliant Blue FCF. Partial separation of Brilliant Blue from Tartrazine is demonstrated immediately following concentration, on a single unpatterned substrate. The mechanism may provide a method for improving the sensitivity of lab-on-paper devices.