Startups often face uncertainty and the potential Valley of Death. To address these challenges, Sustainable Development Goals (SDGs) can serve as a starting point to identify business opportunities in markets driven by SDG-related issues. In this case, we propose using virtual reality (VR) technology as a “painkiller”. This study aims to explore VR use cases and their implications for startup business models and discover a problem–solution fit, i.e., identify the degree to which VR applications effectively address actual problems as “killer applications”. The study employs a customized customer discovery technique, an essential process in the Customer Development methodology. By exploring VR’s applicability in various domains such as entertainment, training, education, and tourism, this study unveils compelling use cases that align with SDG aspects, thus validating the hypothesis on startups’ potential to harness VR for SDG contributions. Furthermore, the study produces VR business model designs based on solutions to SDG-related problems. Thus, startups can function effectively as “painkillers”, offering solutions that are not only desired but urgently needed (problem–solution fit). The implications of these findings extend globally, underlining VR’s role in addressing SDG issues and offering practical insights for startup business model development that are applicable to broader technology adoptions.