Augmented Reality (AR) technology emerges as a transformative tool for on-the-job training, aligning with the Industry 5.0 paradigm that emphasizes human-centric solutions and the integration of digital content into real-industry environments. This study intends to highlight the potential of AR to enhance on-the-job training within the furniture manufacturing industry, motivated by the need for a digital solution to Standard Work (described in Work Element Sheets—WES) training. By adopting a participatory approach, the research project aims to develop an AR-supported Training Interface (TI) to improve training efficiency, user experience, and satisfaction. Adopting an exploratory approach, the first phase of this research (presented in the current paper) characterizes the use-case and employs Hierarchical Task Analysis, semi-structured interviews, and Empathy Mapping to gather in-depth insights about the training needs and workers’ preferences. Results reveal a strong reliance on peer-to-peer training methods and the limited use of traditional printed WES, which lacks visual appeal and interactivity. Focusing on real industry needs and human-centric design, the findings underscore the importance of addressing challenges such as suitability, ergonomic concerns, and user acceptance for successful AR integration in industrial settings.