The current pandemic has modified how education, learning, and technology interact with one another inside universities. The usage of technology for instructional purposes raises the question of whether learning that happens in an online environment is as effective as traditional classroom models. Within this context, this study explores the psychological well-being of students during the COVID-19 pandemic, using an online cross-sectional survey. Data were collected from 246 university students currently studying at a private university in India. Hierarchical regression analysis and structural equation modelling were used to study the mediating effects between communication apprehension, perceived learning, and psychological well-being under the moderating effects of intention to use social media and psychological stress. Results show that higher intentions to use social media alleviated the negative effects of communication apprehension on perceived learning. Interestingly, it was also found that perceived learning had a significant positive relationship with psychological well-being when students experienced higher levels of psychological stress (eustress). Based on the technology acceptance model (TAM) and the transactional theory of stress and coping, we attempt to integrate the findings related to these theories, which can be considered distinct to previous studies. Implications, limitations, and future directions for research and practice have also been discussed.