<p>Formic acid (FA) can be synthesized via the electrocatalytic reduction of CO₂, which yields dilute aqueous FA; its subsequent separation can be facilitated using cyclopentyl methyl ether (CPME) as a solvent. In this case, separation of CPME and FA is required. These separations are typically carried out using distillation columns, which require reliable vapor–liquid equilibrium (VLE) data. In this study, a modified ebulliometer was employed to generate VLE data for the binary system, CPME + FA, under constant-pressure conditions in the ranges of 74.0–101.3 kPa with temperature range of 359.15-379.05 K. The experimentally measured boiling points of the pure components were compared with literature values calculated using Antoine coefficients. The binary VLE data were correlated using the Wilson, NRTL, and UNIQUAC models, and the corresponding binary interaction parameters were determined and reported.</p> Graphical abstract <p></p>