Volatile fatty acids (VFAs), the intermediate of the anaerobic process, are considered to be the critical, high-sensitive and reliable indicators of the process stability. Close monitoring and control of VFAs are paramount for the efficient operation of the anaerobic reactors. In this study, a buffer intensity-based mathematical model was developed, and the least square method was integrated into the model to solve the issue of non-linear fitting of the titration curve. An automatic analyzer embedded with the developed model was designed and implemented for measuring VFAs and alkalinity. Through model optimization, the pH range of 3.5–5.6 was found to be suitable for VFAs analysis. The developed approach was validated by different VFAs (up to 500 mg/L as acetic acid) and carbonate alkalinity concentrations (up to 1500 mg/L as CaCO) with high recovery rates (>0.9). Optimal ratios of carbonate alkalinity to VFAs are identified in the range of 2.4–7.5 for accuracy. Owing to the non-linear fitting of the titration curve, the impact of other weak acid subsystems (e.g., phosphate, ammonium and sulfide) can be negligible. The one-year real-time monitoring of environmental samples by using the automatic analyzer indicates a high consistency and stability compared with the 5 pH point titration. This approach proves to be rapid (<3 min/sample), accurate, reliable and can be applied for real-time automatic monitoring of the anaerobic process.