Large industrial producers consume a huge amount of energy and are a key area of focus for achieving peak carbon and carbon neutrality targets. Based on the operational monitoring of the traditional energy supply system and the transformed PV (photovoltaic)-biogas-gas-electricity system, and the user-side load characteristics and typical daily cooling, heating and the electricity power load scheduling characteristics were analyzed. The annual energy supply data and important energy supply influencing factors of the PV-biogas system were studied, and an evaluation index system for the comprehensive energy system was built, and five factors: PV-biogas system operation status, economic benefits, energy supply quality, environmental benefits and energy efficiency were collaboratively considered, and the comprehensive performance of traditional energy supply system and PV-biogas-gas-electricity system were evaluated. The results show these as follows. Large industrial production enterprises with mainly thermal requirement, typical daily load peaks occur at 09:00—11:00 or 14:00—17:00, the PV-biogas-gas-electricity multi-energy system can meet the cooling, heating and electricity needs of industrial enterprises. The average penetration rate of PV system is less than 10% during non-force majeure hours, and the proportion of gas storage capacity of the biogas system is higher than 50% during normal hours, and the system supply reliability is improved. The evaluation results of a typical case verify the feasibility and validity of the evaluation index system of PV-biogas-gas-electricity multi-energy system, and provide a reference for the comprehensive utilization and coordinated development of PV-biogas-gas-electricity multi-energy system for large industrial enterprises in the future.