Baicalein (the aglycone of baicalin) is a trihydroxyflavone isolated from Scutellaria species, mainly Scutellaria baicalensis Georgi, which is used in Traditional Chinese Medicine to treat cold, hepatic and pulmonary diseases, insomnia, inflammation, hypertension, atherosclerosis, hyperlipidaemia, and dysentery. In scientific literature, baicalein has been extensively reported to exert in vitro and in vivo antioxidant and anti-inflammatory effects, as well as possessing anti-cancer, anti-microbial, immune-modulatory, metabolic, and cardiovascular protection properties. It may modulate a wide array of signaling pathways such as AMPK (5' adenosine monophosphate-activated protein kinase), PPAR-γ (Peroxisome proliferator-activated receptor gamma), Bcl-2 (B-cell lymphoma 2) and Bax (Bcl-2-associated X) proteins, CDKs (Cyclin-dependent kinases), MMP (metalloproteinases), SIRT1, NF-kB (nuclear factor kappa-light-chain-enhancer), EMT (epithelial–mesenchymal transition), TLRs (Toll-like receptors), CPT1 (carnitine palmitoyl transferase-1), and SREBP-1c (sterol regulation element binding response protein-1c). The present review is designed to focus on the potential bioactive activities of baicalein and/or baicalin.