This study investigates polymer/ionic liquid/polymer trilayer membranes for recovering aroma and fragrance compounds from a simplified synthetic model aqueous solution via pervaporation. The membranes featured organophilic polymer layers (PEBA and POMS) sandwiching an intermediate ionic liquid (IL) layer ([P₁₄₄₄][Tf₂N] and [Bmim][Tf₂N]), which were gelled with 12-hydroxystearic acid to ensure structural integrity. The trilayer architecture significantly enhanced separation performance compared with monophase membranes. The PEBA/[P₁₄₄₄][Tf₂N]/PEBA configuration achieved the highest enrichment factors, reaching 1626 for hexanal and 963 for linalool. Meanwhile, the POMS/[P₁₄₄₄][Tf₂N]/POMS system exhibited the highest selectivity relative to water. The introduction of the IL gel layer reduced overall mass transfer resistance while simultaneously suppressing water flux from 0.312 kg h⁻¹ m⁻² (in pure PEBA) to between 0.013 and 0.023 kg h⁻¹ m⁻². Overall, the results demonstrate that combining polymer matrices with gelled ILs in a trilayer design effectively optimizes mass transfer and selectivity, offering a promising strategy for the future valorization of aroma compounds from agro-industrial aqueous streams.