One of the key challenges in the promotion of web-based learning is the development of effective collaborative learning environments. We posit that the structuration process strongly influences the effectiveness of technology used in web-based collaborative learning activities. In this paper, we propose an ant swarm collaborative learning (ASCL) environment based on a swarm intelligence system (SIS) that structures opportunities for effective collaboration and learning in a dynamic way. The results of our experiments indicate that: (1) the self-organizing behavior of SIS is positively associated with system appropriation; (2) the multi-agent-based mechanism of SIS is positively associated with system appropriation; (3) the cohesive capability of SIS is positively associated with system appropriation; and (4) the learner's tendency toward system appropriation is positively associated with learning effectiveness. Our findings also show that learners in an ASCL environment outperform their counterparts in a general web-based learning (GWL) environment. We conclude that different types of technological support can influence the achievement in a web-based learning environment. (Contains 9 tables and 3 figures.)