Negative thermal expansion (NTE), whereby lattices contract upon heating, is of considerable interest for its wide applications in many fields. Molecular materials have been widely investigated as catalysts, sensors, etc., which usually endure temperature vibration. NTE can become a substantial means for controlling the coefficients of thermal expansion. Molecular materials possess plentiful structures and can be easily decorated, making them ideal platforms for thermal expansion modification. In this feature article, we provide an overview of the recent developments in utilizing NTE in molecular materials and summarize some mechanisms leading to NTE. The discussion of NTE in molecular materials concerns many factors, including transverse vibration, geometric flexibility, host-guest interactions, spin crossover, molecular packing rearrangement and molecular conformational changes.