This paper addresses the need to understand the social dynamics of multiple users collaborating in a Virtual Reality (VR) environment. Specifically, we investigate whether the physiological synchrony between leader-follower task roles in Collaborative Virtual Environments is influenced by the user's previous experience and background. Physiological synchrony is a measure of spontaneous temporal coordination or interdependency between the physiological activity of two or more individuals. Electrodermal activity signals from 8 pairs of users were collected and processed using two different algorithms to measure their synchronization. The results show that physiological synchrony has a moderate correlation with task completion time in VR. Also, the Dynamic Time Warping (DTW) algorithm is more effective in computing synchrony. The findings show correlations between DTW distance, and task performance measures (completion time, and pre-construct scores).