Extended Reality (XR) is increasingly being used in technical education and training, but its impact on students’ cognitive and emotional factors remains an open question. This study compared XR-based and traditional paper-based learning methods in the context of pneumatic circuit assembly. The main objectives were to evaluate the differences in task performance, cognitive responses (self-confidence), emotional responses (frustration, anxiety, concentration), and perceived user experience between the two approaches. Eighteen higher education engineering students participated in a between-subjects study as part of the XREN Erasmus+ project. One group studied circuit assembly using traditional materials, while the other trained with an interactive XR application. After the learning phase, participants completed a hands-on task in a real laboratory, followed by self-reported ratings of their emotional and cognitive states. The results did not report differences in task performance or most of the cognitive and emotional variables measured between the two groups. However, frustration levels were higher among students who received XR training, suggesting that emotional factors should be carefully considered when integrating immersive technologies into learning environments. Nonetheless, students reported good user experience scores with respect to the XR application. Future research should explore repeated exposure to XR and propose strategies to mitigate frustration while maintaining engagement, ultimately refining XR-based learning experiences for engineering education.