Three-dimensional (3D) Fe/SiC monoliths with parallel interconnected channels and different cell geometries (square, troncoconical, and triangular) were manufactured by robocasting and used as catalytic reactors in hydroxylation of phenol using hydrogen peroxide to produce dihydroxybenzenes; the reaction was performed at C phenol,0 = 0.33 M, C phenol,0 :C H 2 O 2 ,0 = 1:1 M, W R = 3.7 g, T = 80−90 °C, and τ = 0−254 g cat •h•L −1 with water as a solvent. The values of the apparent kinetic rate constants demonstrated the superior performance of the triangular cell monoliths for hydrogen peroxide decomposition , phenol hydroxylation, and dihydroxybenzene production reactions. A computational fluid dynamic model was validated with the experimental results. It demonstrated that the triangular cell monoliths, with a lower channel hydraulic diameter and not-facing interconnections, provided a higher internal macrotortuosity that induced an oscillating flow of the liquid phase inside the channels, leading to an additional transverse flow between adjacent parallel channels. This behavior, not observed in the other two geometries, resulted in a better overall performance.