The increasing demand for online sensors applied to advanced control strategies in water resource recovery facilities has resulted in the increasing investigation of fault-detection methods to improve the reliability of sensors installed in harsh environments. The study herein focuses on the fault detection of ammonium sensors, especially for effluent monitoring, given their potential in ammonium-based aeration control applications. An artificial neural network model was built to predict the ammonium content in the effluent by employing the information from five other sensors installed in the activated sludge tank: NH4+, pH, ORP, DO, and TSS. The residual between the model prediction and the effluent ammonium sensor signal was utilized in a fault-detection mechanism based on principal component analysis and Shewhart monitoring charts. In contrast to previous studies, the present work utilizes typical faults collected from a 1 year historic dataset of an actual sensor setup. Treatment process anomalies, calibration bias faults, and fouling drifts were the most common issues identified from the historic dataset, and they were promptly identified by the proposed fault-detection methodology. Once a fault is detected, the model prediction can be actively used in place of the sensor for process control without affecting the treatment process by utilizing faulty datasets.