An easy one-step synthesis of carbon monoliths with hierarchical porosities was developed by combining resorcinol and formaldehyde sol-gel polycondensation with soft-templating method (use of amphiphilic surfactant Pluronic F127 as a mesopores template). By varying the synthesis conditions of polycondensation, purely microporous, micro-mesoporous and micro-meso-macroporous carbon monoliths were obtained. It was found that micropores and mesopores arise during the carbonization while macropores formation occurs during the gelling step through a controlled macroscopic phase separation process. The obtained set of model porous materials allowed to evidence and quantify the significance of mesopores and macropores for adsorption kinetics (from both gas and liquid phase) of materials having micropores. The ability of CO2 to diffuse (at 30 °C) through the ultramicroporous network was not affected by presence of meso- and macropores. On the other hand, mesopores were found to be crucial for successful diffusion of N2 (at -196 °C) into ultramicropore network of carbon monoliths. For adsorption from liquid media, both mesopores and macropores present in the templated samples were found to be of primary significance for fast kinetics of adsorption. The only presence of ultramicropores did not enable the diffusion of neither phenol nor methylene blue to the active sites. At the opposite, the presence of mesopores allowed the diffusion of both species from mesopores to micropores. Diffusion was further improved by the presence of extra macropores. These results were proved by calculation of the effective diffusion parameter based on the Crank´s intraparticle diffusion model. Developed synthesis principles are expected to be a basis for preparation of hierarchically porous carbon for various applications (water and air depollution, electrochemical energy storage, catalysis) from other precursors (e.g. liquefied biomass).