Organic materials have gained considerable attention for electrochromic (EC) applications owing to improved EC performance and good processability. As a class of well-recognized organic EC materials, viologens have received persistent attention due to the structural versatility and property tunability, and are major active EC components for most of the marketed EC devices. Over the past two decades, extensive efforts have been made to design and synthesize different types of viologen-based materials with enhanced EC properties. This review summarizes chemical structures, preparation and EC properties of various latest viologen-based electrochromes, including small viologen derivatives, main-chain viologen-based polymers, conjugated polymers with viologen side-chains and viologen-based organic/inorganic composites. The performance enhancement mechanisms are concisely discussed. The current marketed viologens-based electrochromic devices (ECDs) are briefly introduced and an outlook on the challenges and future exploration directions for viologen-based materials and their ECDs are also proposed.