Résumé : The neural mechanisms that support naturalistic learning via effective pedagogical approaches remain elusive. Here we used functional near-infrared spectroscopy to measure brain activity from instructor-learner dyads simultaneously during dynamic conceptual learning. Results revealed that brain-to-brain coupling was correlated with learning outcomes, and, crucially, appeared to be driven by specific scaffolding behaviors on the part of the instructors (e.g., asking guiding questions or providing hints). Brain-to-brain coupling enhancement was absent when instructors used an explanation approach (e.g., providing definitions or clarifications). Finally, we found that machine-learning techniques were more successful when decoding instructional approaches (scaffolding vs. explanation) from brain-to-brain coupling data than when using a single-brain method. These findings suggest that brain-to-brain coupling as a pedagogically relevant measure tracks the naturalistic instructional process during instructor-learner interaction throughout constructive engagement, but not information clarification.