Unprecedented mismatch occur frequently in the photovoltaic (PV) array systems, challenging the classical monitoring systems. However, the study of artificial intelligence methods lacks some well-designed experiments for a systematic verification because mismatch are influenced by many aspects such as the PV array, the DC–DC converter, the DC–AC inverter, the loads as well as the environmental variables. The objective has two folds. One is to design some identical apparatuses to emulate the ‘same’ real-world solar power station that is operated under multiple mismatch for a controllable, repeatable and comparable experimental study. Another is to propose a novel condition monitoring strategy based on the backward propagation neural network and a decision-making formula. Some controllable indoor experiments and uncontrollable outdoor experiments are carried out to verify the ideas. Such work has never been studied before. The experimental results show that the derived monitoring systems identify and classify accurately different mismatch in both indoor tests and outdoor experiments. Moreover, real-time experimental results infer that the data-driven approach with the self-learning capabilities is adaptive to the environmental changes. Therefore, the supervised learning-based condition monitoring strategy is promising in the solar power industry in terms of operation management and performance enhancement.