Non-intrusive load monitoring (NILM) technology, crucial for intelligent electricity management, has gained considerable attention in residential electricity usage studies. NILM enables monitoring of total electrical current and voltage in homes, offering insights vital for enhancing safety and preventing domestic electrical accidents. Despite its importance, accurately discerning the operational status of appliances using non-intrusive methods remains a challenging area within this field. This paper presents a novel methodology that integrates an advanced clustering algorithm with a Bayesian network for the identification of appliance operational states. The approach involves capturing the electrical current signals during appliance operation via NILM, followed by their decomposition into odd harmonics. An enhanced clustering algorithm is then employed to ascertain the central coordinates of the signal clusters. Building upon this, a three-layer Bayesian network inference model, incorporating leak nodes, is developed. Within this model, harmonic signals are used as conditions for node activation. The operational states of the appliances are subsequently determined through probabilistic reasoning. The proposed method’s effectiveness is validated through a series of simulation experiments conducted in a laboratory environment. The results of these experiments (low mode 89.1%, medium mode 94.4%, high mode 92.0%, and 98.4% for combination) provide strong evidence of the method’s accuracy in inferring the operational status of household electrical appliances based on NILM technology.