Novelty has recently been suggested as a potential basic psychological need within self-determination theory. Taking into account the lack of research on this new construct, the purpose of this study was to show the role of novelty satisfaction in physical education, analyzing its relations with some outcomes that are relevant for academic achievement. Secondary school students completed measures of basic psychological need satisfaction (autonomy, competence, and relatedness), novelty satisfaction, the three types of intrinsic motivation (to know, to accomplish, and to experience stimulation), and different outcomes (vitality, dispositional flow, and satisfaction) for physical education. Confirmatory factor analysis showed a high correlation between autonomy and novelty satisfaction. The problem of discriminant validity was solved by removing an item from the original version of the Novelty Need Satisfaction Scale due to its overlap with the autonomy construct. This modification contributed to improving the psychometric properties of this scale. Structural equation modeling showed that satisfaction of the need for competence was the strongest predictor of intrinsic motivation to accomplish and to experience stimulation, whereas novelty satisfaction was the strongest predictor of intrinsic motivation to know. Positive direct and indirect effects from novelty satisfaction were found on vitality, dispositional flow, and satisfaction with physical education classes. These results suggest the importance of teachers developing strategies to provide novelty support, with the aim of achieving multiple positive outcomes in physical education.