This systematic review comprehensively explores the integration of Extended Reality (XR) technologies, comprising Virtual Reality (VR), Augmented Reality (AR), and Mixed Reality (MR), into New Zealand’s STEM education framework. In alignment with PRISMA 2020 guidelines, we systematically analyzed 127 peer-reviewed studies from the Web of Science (n = 48), Scopus (n = 57), and Dimensions (n = 22) and incorporated 15 grey literature sources, resulting in 142 studies included in the review. Our meta-analysis found substantial improvements in student conceptual understanding from XR-enhanced STEM modules. Specifically, we observed an average increase of 23.4% when compared to traditional instructional methods (95 percent Confidence Interval: 18.7 to 28.1 percent, p < 0.001). These gains were especially prominent in interactive learning environments where immersive XR applications supported deeper engagement and the visualization of abstract STEM concepts. The qualitative synthesis highlighted several key barriers that limit effective XR integration. These include technological infrastructure gaps reported in 68 percent of reviewed studies, a critical need for educator training cited by 82 percent of studies, and curriculum alignment issues present in 57 percent of cases. Methodological quality was assessed using the Mixed Methods Appraisal Tool (MMAT) 2018, and the qualitative component employed a deductive thematic coding approach with inter-coder reliability verification. Successful institutional implementations were also identified. At Auckland University of Technology, XR-supported courses produced a 67 percent increase in student engagement, while Wellington High School achieved a 41 percent reduction in STEM achievement gaps through targeted XR interventions. Based on the evidence, we propose a four-phase implementation framework that addresses the technological, pedagogical, and policy requirements for sustainable XR adoption. These findings highlight the role of immersive technologies in supporting human-centered digital transformation and future skills development in the transition to Industry 5.0. The review contributes evidence-based insights that support the transition from technology-driven approaches associated with Industry 4.0 to the human-centered, socially oriented priorities of Industry 5.0. It also identifies critical research gaps, particularly in long-term learning outcomes and the integration of Mātauranga Māori within XR-enabled STEM environments.