The significance of higher-order thinking (HOT) is becoming increasingly prominent in the twenty-first century, as reflected in the framework of most recent competency models. Blended learning models are universally recognized as promising endeavors to promote learners' HOT in the contemporary higher education field. To ensure that such learning models function as intended, a thorough and systematic study is required to determine the variables that most influence learners' development of HOT in a blended learning environment. A sample of 422 Chinese vocational college students with blended learning experience completed a survey in which their perceptions of teaching presence, social presence, self-regulated learning (SRL), information and communication technology (ICT) self-efficacy, and HOT were measured. Structural equation modeling (SEM) revealed that students' SRL directly and significantly influenced their HOT in a blended learning environment. Furthermore, teaching presence, social presence, and ICT self-efficacy all indirectly affect HOT through their impact on SRL. Based on these findings, this study recommends that instructors teaching in a blended learning environment should focus on improving learners' SRL abilities, social interaction techniques, ICT competencies, and teaching presence to help learners develop HOT.