In this paper, the obtaining, characterization and testing of a new electrocatalyst composite electrode based on multi-wall carbon nanotubes and silver-exchanged natural zeolite (MWCNT-AgZ) for non-enzymatic oxidation and determination of glycerol is reported. The electroanalytical sensitivity for the determination of glycerol at the MWCNT-AgZ electrode ranged from 0.051 to 0.386 mA/mM as a function of the electrochemical technique used, and the highest sensitivity was reached for linear-sweep voltammetry. The recovery studies indicated the possibility to determine glycerol in real samples.