Natural fibers, derived from plants such as wood, hemp, straw and cotton, have been explored for the fabrication of porous structures for thermal insulation applications due to their widespread availability, sustainability, and cost-effectiveness. Understanding the fundamental heat transfer mechanisms within natural fiber-derived porous structures is crucial for both optimized geometric design and real-world insulation applications. Herein, we developed a theoretical framework considering geometric parameters, including pore size, fiber diameter and porosity (i.e., density), to examine the contribution of various heat transfer modes (i.e., conduction, convection, and radiation) on the effective thermal conductivity of porous structures derived from natural fibers. Our results indicate that thermal radiation is largely responsible for the rapid increase in effective thermal conductivity of the natural fiber-derived porous insulations in low-density regions (< 50 kg/m³) and that natural convection rarely occurs within these materials. The insulation materials derived from natural fibers with diameters in the micron range (5–50 μm) can achieve their minimum thermal conductivity at an optimal density of 50–90 kg/m³. Effective strategies to lower the effective thermal conductivity of natural fiber-derived porous materials include increasing porosity to curtail solid conduction, incorporating nanoscale pores by using nanosize fibers to diminish gaseous thermal conductivity. This research offers valuable insights into the heat transfer mechanisms in natural fiber-derived materials and should guide the structural design and optimization process toward developing super-thermal insulation materials derived from natural fibers.