In the context of demand response (DR), formulating rational electricity pricing (EP) and electricity pricing subsidy (EPS) strategies is crucial for the power grid when dealing with a high electricity user (EU), particularly an electrolytic aluminum enterprise (EAE) in an industrial park (IP). In addition, it is difficult to assess the response effectiveness of EU. This paper proposes a method to assess demand response willingness (DRW) by introducing indicators such as demand response economy and demand response potential, while taking into account carbon emission deviation. Then, the EPS is formulated based on the result of the DRW assessment. Second, this paper establishes a two-layer electricity supplier (ES)-EAE game model, in which the ES operates as the leader and EAE operates as the follower. The model takes into account the fluctuation and deviation of loads, constructs utility functions for both the leader and follower, selects dynamic EP scenarios at different time scales, and employs a large-scale global optimization particle swarm algorithm based on cooperative evolution for solving. Finally, the model's effectiveness is validated under three electricity pricing strategies: peak-valley pricing, critical peak pricing (CPP), and real-time pricing (RTP). According to the result of simulations, under the RTP strategy, the DRW of EAE has increased by 12.5% compared to the CPP strategy, and the DR load has increased by 82%. Additionally, there has been some reduction in costs of electricity consumption. This indicates that the ES can effectively guide the EU to reduce peak loads through EP, and the EU can also achieve a reasonable reduction in electricity costs.