Metacognition may be defined as the knowledge and regulation of one’s own cognitive system, the capacity to reflect about one’s actions and thoughts. Current views on metacognition pose it as a fundamental factor in achieving autonomy in learning, and promoting deep understanding and problem-­solving skills. This relevance has in turn led to interest in creating learning experiences conducive to developing the use of metacognition, especially in science education. Despite this increasing interest, progress has been hindered by the inherent difficulties associated with developing assessment methods for metacognition. Consequently, evidence for the efficacy and effectiveness of learning environments in promoting metacognition has been scarce. In this article we present some of the work that our research group has done to contribute in addressing this problem. We report the development and validation of an automated and rapid multi-­methods strategy to assess regulatory metacognition in chemistry problem solving from large numbers of participants. This strategy combines two separate instruments: one prospective, the Metacognitive Activities Inventory (MCAi) and one concurrent, the Interactive MultiMedia Exercises (IMMEX). Additionally, we describe two interventions that by using the multi-­ methods assessment strategy have been demonstrated to enhance metacognition use and problem solving ability. The first intervention is a cooperative problem-­based general chemistry laboratory; this study presents evidence that links participation in the laboratory with development of higher order skills. The second instantiation is a two-­week collaborative problem solving activity. Findings from a phenomenological approach nested within a mixed-­methods design suggest that meaningful, purposeful social interaction and reflective prompting act as promoters of metacognition development in both learning environments. These factors are not exclusive to the interventions and we maintain that they are transferable and may be embedded by practitioners in their instruction. This report presents the development and validation of metacognition assessment methods and studies of the efficacy of learning experiences in developing metacognition.