Membraneless organelles (MLOs) can assemble via liquid–liquid phase separation (LLPS). Here, we review the metastable MLOs driven by LLPS, from multifaceted regards including energy state, molecular interactions, molecular structure, phase transition, and the associations with diseases, to advance the insight into properties and pathogenesis associated with LLPS of biological matter. Read the article here: https://onlinelibrary.wiley.com/doi/abs/10.1002/appl.202300071.