A significant number of De facto orphans in underdeveloped regions face potential mental health risks, while some novel interventions attempt to involve university student volunteers in providing companionship. However, there is little documented literature on current practices of such emotional support volunteer activities. We conducted a comprehensive investigation of multiple stakeholders involved in an online companionship program facilitated by university student volunteers, designed to provide remote emotional support to these children. Through field observations and interviews, we summarize current practices and identify benefits. We discovered that current remote volunteer initiatives face numerous challenges impeding companionship effectiveness. We summarized four potential technological requirements derived from these challenges. Our study provides the first documented account of remote volunteer companionship activities aimed at improving vulnerable children’s mental health. Our research can inspire future developments of technological solutions for improving emotional companionship in volunteer programs and vulnerable children’s wellbeing.