The cave automatic virtual environment (CAVE) can provide a large-scale immersive and interactive virtual reality (VR) learning environment, which is suitable for the navigation of visualized learning objects and communication among teachers and students. Its applications have gained attention in the field of architecture, engineering, and construction (AEC). This empirical study aimed to examine the effects of the CAVE-VR learning environment on enhancing students' perception of essential building elements compared with the traditional learning environment and explore the factors influencing students' technology acceptance of this teaching innovation. Initially, the study developed teaching materials related to essential building elements on the CAVE-VR system and implemented the teaching innovation in an undergraduate course, Introductory Construction Technology and Materials. A two-round comparison was adopted in this study to evaluate the effects of the innovative learning environment created by the CAVE-VR system and the traditional learning environment using slides projected on the whiteboard. Two in-class quizzes were designed to test students' comprehension of essential building elements; a questionnaire survey, which was devised based on the cognitive load theory and technology acceptance model, was utilized to evaluate students' attitudes toward the learning experience. According to the descriptive and statistical analysis of the quiz results and questionnaire survey responses, the findings of this empirical study are as follows: (1) for the first-round implementation, it was found that students learning through the proposed CAVE-VR environment attained an enhanced perception of the building elements compared with students learning through the slides; for the second-round implementation, it was detected that the perception of building elements of students learning through the CAVE-VR environment for a second time was significantly enhanced compared with students learning through the CAVE-VR environment for the first time; (2) based on the descriptive analysis of students' responses to the questionnaire survey, most students held a positive technology acceptance attitude toward the immersive CAVE-VR learning environment and experienced a moderate level of cognitive workload to complete their learning tasks, facing few difficulties in interactive operations; and (3) according to the statistical analysis of the feedback of students from different learning programs, Higher Diploma students experienced a significantly lower degree of time pressure, effort demand, and sense of accomplishment than Bachelor students in the CAVE-VR learning environment; at the same time, students from both learning programs considered that the perceived usefulness had a direct impact on their intention to use the CAVE-VR learning environment.