Blended learning (BL) combines online and face-to-face teaching and learning and is thought to be an effective means to cultivate learners’ sustainability literacy. The success of BL relies on learners who take the initiative to participate in the learning process. Therefore, this study aims to examine learners’ acceptance of the BL system. The technology acceptance model (TAM) and the self-efficacy theory are combined to construct a systematic model to determine the learners’ continuous intention to adopt BL. Seven constructs are identified, i.e., course quality (CQ), technical support (TS), perceived usefulness (PU), perceived ease of use (PEOU), satisfaction (SE), self-efficacy (SE), and behavioral intentions (BI). A survey was conducted using a close-ended questionnaire, and 461 valid responses were collected from Huaqiao University’s undergraduate students. Covariance-based structural equation modelling was performed. The empirical findings show that except for the hypothesis regarding the connection between PU and PEOU, all the other hypotheses are verified. CQ stands out as having the greatest positive effect on PEOU, which highlights the importance of CQ for BL. The study also confirms that PU significantly impacts SA, SE, and BI, and both SA and SE significantly influence BI. Based on these results, some suggestions are provided for educators and administrators as to how to better design BL systems to strengthen sustainability education.