Synchronous online learning via technology has become a major trend in institutions of higher education, allowing students to learn from video lectures alongside their peers online. However, relatively little research has focused on the influence of these peers on students' learning during video lectures and even less on the effect of peer familiarity. The present study aimed to test the various effects of peer presence and peer familiarity on learning from video lectures. There were three experimental conditions: individual-learning, paired-learning with an unfamiliar peer, and paired-learning with a familiar peer. ANCOVA results found that students paired with a familiar peer reported higher motivation in learning and more self-monitoring behaviors than those paired with an unfamiliar peer or who learned alone. Furthermore, students paired with both unfamiliar or familiar peers demonstrated better learning transfer than those who learned alone. Together, these results confirm the benefits of and support learning alongside a familiar peer during video lectures.