In this paper, the fabrication, surface characterisation and electrochemical properties of graphite flake (GFPE) and multilayer graphene (MLGPE) paste electrodes are described. The Raman investigations and scanning electron microscopy were used to analyze and compare structure of both carbon materials. The electroanalytical performance of both electrodes was examined and compared on the basis of the square-wave and cyclic voltammetric behavior of acetaminophen and model redox systems. Results of those studies revealed that GFPE has a larger electroactive surface area and better conductive properties, whilst MLGPE demonstrate better analytical characteristic in case of acetaminophen (AC) determination. AC determination was developed using square wave voltammetry (SWV) and square wave stripping voltammetry (SWSV). For both working electrodes, the process of accumulation enabled us to obtain an extended linear range and to lower the detection limit. In pharmaceutical formulations, AC was determined with good recovery.