This study not only sheds light on the unique potential of bismuth in halogen bonding but also paves the way for further explorations into the realm of heavy main group elements. The findings underscore the utility of comprehensive computational and experimental investigations to truly understand the potential of these unique elements in molecular chemistry. Furthermore, the results emphasize the importance of considering alternative oxidation states and molecular frameworks to unlock unexpected bonding and reactivity avenues, as evident from the successful employment of the Bi(I) state in halogen bonding. As the field continues to grow and diversify, we anticipate that the learnings from this study will serve as a foundational reference, inspiring chemists to explore the uncharted territories of main group element chemistry.