The degradation rate of Volatile Fatty Acids (VFAs) produced predominantly in the acidogenesis stage is a key process parameter to be optimised to ensure a successful Anaerobic digestion (AD). Thermodynamically, the oxidation of the VFAs are energetically unfavourable, and as such external energy source apart from the energy derived from the hydrolysis of Adenosine Triphosphate (ATP) is needed for the initial activation of the VFAs, initial growth of the methanogens in AD process and improved degradation rate of the VFAs. Thus, this research investigated the influence of polyphosphate hydrolysis on the degradation rate of the VFAs at high concentration. Sodium-propionate, Sodium-butyrate and Sodium-acetate salts were added at the start of experiments in order to increase the concentration of the VFAs. The polyphosphate salts used were; Na-hexametaphosphate, Na-tripolyphosphate and potassium pyrophosphate. The control experiment was polyphosphate free and three process parameters (degradation rate, cumulative biogas production and specific methane content) of anaerobic digestion were investigated. The experiments were carried out at a mesophilic temperature of 37.5°C for 41 days. The results of the investigation showed that the treated reactors with the polyphosphate salt solution in low concentration performed better than the reactors with high concentration of the polyphosphate salts solution. All the treated reactors with poly-P salts performed better than reactor Nr-9 (control experiment), but reactor Nr-1 was outstanding with an improved degradation rate of 47%, cumulative biogas production of 21% and specific methane content of 23%.