Introduction: Sorbic acid (SA) is widely applied as an antimicrobial preservative in processed foods, but its reliable determination remains difficult when complex matrices interfere with direct instrumental analysis. Conventional steam distillation can remove these interferences, although the procedure is time-consuming, equipment-intensive, and poorly suited for rapid or high-throughput food testing. Methods: Here, a poly(methyl methacrylate) (PMMA)-based microfluidic distillation system was developed for rapid sorbic acid separation prior to HPLC-PDA determination. The chip integrates a sample reservoir, buffer channel, condensation microchannel, and distillate collection zone within a compact, thermally controlled platform. Unlike earlier micro-distillation chips developed for formaldehyde, sulfur dioxide, or propionic acid, the present device introduces an SA-oriented vapor-buffering layout and a thermally separated condensation path. Numerical simulations guided the chip layout and thermal design, confirming stable heating and cooling zones at approximately 120 °C and 4 °C, respectively, with simulated temperatures differing from experimental measurements by less than 3%. Results: Operating parameters were optimized experimentally. Maximum distillation performance was obtained at a steam pressure of 4 bar, a distillation time of 30 min, and a condensation channel width of 2.5 mm, yielding distillation efficiencies close to 98%. Validation using sorbic acid standards from 50 to 2500 mg/L showed strong agreement with conventional steam distillation, with an R2 of 0.9964 and a mean relative accuracy of 95.68 ± 3.8%. Additional precision, device-to-device reproducibility, and matrix-effect tests confirmed acceptable repeatability and chip-to-chip consistency. Application to commercial food samples yielded relative accuracies of 92%–107% compared to the TFDA/CAAPIC reference workflow, with deviations below 8% and a limit of detection (LOD) of 60 mg/L. Discussion: The resulting platform establishes an SA-oriented micro-distillation pretreatment strategy that combines vapor-buffered chip design, simulation-guided thermal management, and complex-matrix validation for food safety analysis.