In the age of Industry 5.0 (I 5.0), manufacturing SMEs face the critical challenge of balancing technological advancement with environmental sustainability. This study explores the intricate relationships between Industry 5.0 technologies—specifically Big Data Analytics and Artificial Intelligence (BDA-AI), Human-Robot Collaboration (HRC), and the Internet of Things (IoT), and sustainable practices in manufacturing SMEs. Drawing on data from 466 SMEs across key industrial regions, we employ structural equation modeling to uncover the transformative roles of Eco-Innovation. Our findings reveal that Eco-Innovation (Eco-Inn) acts as a pivotal mediator, translating technological capabilities into enhanced environmental performance (EP). This study breaks new ground by examining the ethical implications of Human-Robot Collaboration within Industry 5.0, offering insights into its long-term sustainability impact. By integrating the resource-based view theory, this research presents a novel framework for sustainable manufacturing SMEs in the digital era.