In the wake of Industry 4.0, the ubiquitous internet of things provides big data to potentially quantify the environmental footprint of green products. Further, as the concept of Industry 5.0 emphasizes, the increasing mass customization production makes the product configurations full of individuation and diversification. Driven by these fundamental changes, the design for sustainability of a high-mix low-volume product–service system faces the increasingly deep coupling of technology-driven product solutions and value-driven human-centric goals. The multi-criteria decision making of sustainability issues is prone to fall into the complex, contradictory, fragmented, and opaque flood of information. To this end, this work presents a data-driven quantitative method for the sustainability assessment of product–service systems by integrating analytic hierarchy process (AHP) and data envelopment analysis (DEA) methods to measure the sustainability of customized products and promote the Industry 5.0-enabled sustainable product–service system practice. This method translates the sustainability assessment into a multi-criteria decision-making problem, to find the solution that meets the most important criteria while minimizing trade-offs between conflicting criteria, such as individual preferences or needs and the life cycle sustainability of bespoke products. In the future, the presented method can extend to cover more concerns of Industry 5.0, such as digital-twin-driven recyclability and disassembly of customized products, and the overall sustainability and resilience of the supply chain.