Understanding physical phenomena related to fluid flow transport in plants and especially through wood is still a major challenge for the scientific community. To this end, we have focused our attention on the design of wood-mimicking polymeric architectures through a strategy based on the double porogen templating approach which relies on the use of two distinct types of porogens, namely aligned nylon threads and a porogenic solvent, to produce macro- and nanoporosity levels, respectively. A bio-based phenolic functional monomer, i.e., vanillin methacrylate, was employed to mimic either hard wood or soft wood. Upon free-radical polymerization with a crosslinking agent in the presence of both types of porogenic agents, followed by their removal, biporous materials with anistotropic tubular macropores surrounded by a nanoporous matrix were obtained. They were further fully characterized in terms of porosity and chemical composition via mercury intrusion porosimetry, scanning electron microscopy and X-ray microtomography. It was demonstrated that the two porosity levels could be independently tuned by varying structural parameters. Further, the possibility to chemically modify the pore surface and thus to vary the material surface properties was successfully demonstrated by reductive amination with model compounds via Raman spectroscopy and water contact angle measurements.