Selective production of phenols via ex-situ catalytic pyrolysis of lignocellulosic biomass is a promising route in biomass conversion. Therefore, developing a low-cost and effective catalyst for this process has emerged as an important topic. Here, the iron nanoparticles-based carbonaceous catalysts were prepared via combining hydrothermal carbonization and pyrolysis approach and first used in the catalytic microwave-assisted pyrolysis of torrefied corn cob for phenols production. The effects of catalyst types, catalytic temperature, and catalyst to feedstock ratio on the production of phenolic compounds were studied. The total selectivity of phenols can reach 91.07 area% with the total yield of 18706.6 µg/ml bio-oil using the FeHC@ hydrochar catalyst (prepared by hydrothermal carbonization in the Fe(NO3)3 solution and pyrolysis) at the catalytic temperature of 450 °C and catalyst to feedstock ratio of 5:10. After using seven times, partial loss of catalytic activity of FeHC@hydrochar was found. This study also presented unique insights into the deactivation of carbonaceous catalysts, showing that sintering, oxidation of α-Fe and Fe3C phases, active site coverage, and pore blockage were the causes of the reduction of catalytic performance. Regeneration experiments showed that it is impracticable to calcine deactivated catalyst at an inert atmosphere and more advanced techniques needed to be developed to solve this problem. Overall, this study can provide a reference for realistic scale-up production of renewable phenols.