A new class of porous membranes is introduced to provide unique separation mechanisms by surface interactions and capillary condensation. High-performance architectural surface selective (HiPAS) membranes were designed for high perm-selective flux and high-temperature tolerance for hot vapor processing and liquid processing. Due to surface-enhanced selectivity, larger-fluxes were achieved by utilizing larger pore sizes (similar to 8 nm for vapor phase and micron-sized pores for liquid phase separations). This article describes a membrane-based separation concept for biomass conversion pathways and demonstrates the initial data for selective permeation of toluene-water and toluene-phenol-water relevant to biofuel processing.