Phenolic resin has been widely used owing to its excellent thermal insulation performance. However, the application of phenolic resin in the field of geopolymer remains unexplored. Here, the foamed fly ash geopolymer samples with high porosity were prepared using phenolic resin for the purpose of foaming materials. The thermal insulation properties of these samples were evaluated by Transient Plane Source Method, and the effect of phenolic resin on pore characteristics was investigated by Mercury Intrusion Porosimetry (MIP), aim to explore how phenolic resin affects the thermal conductivity by changing the pore characteristics of geopolymer. In addition, considering that the internal gas thermal conductivity of pores with different pore sizes is also different (Knudsen effect), in order to predict the thermal conductivity more accurately, this research proposes an iterative calculation method to establish a thermal conductivity model. The results show that phenolic resin can improve the thermal insulation effect of geopolymer, and the minimum thermal conductivity of the sample is 0.17 W/m·K. In addition, according to the test results of MIP, it can be found that phenolic resin mainly promotes the porosity of micron pores (>1 μm) whereas there is slight inhibition on nano pores (<1 μm), but the beneficial effect of the increase of micron-sized pores (>1 μm) on the thermal insulation performance of geopolymer is greater than the negative influence effect of the disappearance of nano pores. Moreover, according to the results of MIP, phenolic resin can narrow the throat in the pore of the ink bottle, limit the thermal convection of the gas between the pores, and reduce the thermal conductivity. Finally, the newly modified Russell model considering the Knudsen effect can effectively predict the thermal conductivity by using the experimental data. This study provides a new method to improve thermal insulation performance of geopolymers and offers a new building insulation product.