Perovskite nanocrystals (PNCs) and their strongly confined versions have traditionally been synthesized via hot injection methods. However, there is a pressing need for a new synthesis method that offers more flexible surface chemistry, improved optical properties, and greater sample stability. Here we explore and exploit the recently introduced microwave (MW) synthesis method, focusing on temperature and coating ligands, including a polymer ligand for which the hot injection method is unsuitable. The optimized microwave synthetic protocols produce PNCs with better exciton definition, lower polydispersity, and stronger ligand attachment than their hot injection counterparts. A variety of characterization techniques were employed to compare the properties of PNCs produced by the hot injection versus microwave methods. Insight into the molecular basis for the improved PNC properties was provided by FTIR and several NMR experiments that revealed the nature of the attachment of different ligands and their interactions with the PNCs. The overall results demonstrate that MW synthesis is a promising alternative to the HI method, particularly if smaller PNCs with strong quantum confinement are desired.