The excess of glycerol as a by-product of biodiesel has become an obstacle in the biodiesel production chain, creating new challenges for its sustainable use. Thus, the use of hierarchical zeolites to obtain higher value-added products from glycerol is a promising alternative, due to its properties such as high specific area, acidity, shape selectivity, with a shorter diffusion path in the micropores and an improved access to micropores through the generated mesopores. Thus, the objective of this work was to generate mesopores in the zeolites *BEA, EMT and FAU by an economical and easy method, and to evaluate their catalytic activity in the glycerol dehydration reaction, and to obtain Zeolite Templated Carbon - ZTC in order to obtain higher added value products. Zeolites were hierarchical by post-synthesis treatment. EMT zeolite was first hierarchical with NH4F. *BEA zeolite was hierarchical with NH4OH, hierarchical zeolites were applied in the glycerol dehydration reaction showing excellent conversion (EMT 60.83% and Beta 99.58%), being selective to acetaldehyde, acrolein and acetol. The ZTCs were obtained using the hierarchical FAU zeolite and glycerol as a precursor for the first time. Glycerol presented itself as an innovative and efficient precursor for obtaining ZTC.