The study on Cephalotaxus sp. dates back to the early 19th century. Many bioactive components have been isolated and elucidated from this genus, especially the cephalotaxine-type alkaloids (CTAs), which displayed potent inhibition against cancer cells. In particular, Homoharringtonine (HHT) and isoharringtonine (IHT) exhibited potent antiproliferative activities against murine P-388 leukemia cells with IC₅₀ values of 17 and 18 nM, respectively. HHT (drug name: omacetaxine mepesuccinate) had been approved by the Food and Drug Administration (FDA) for the treatment of chronic myeloid leukemia in the chronic phase (CP) or accelerated phase (AP). Additionally, the unique pentacyclic skeleton of CTAs attracted much attention with regard to its synthesis, and many significant advances have been achieved in recent decades, especially in the field of asymmetric synthesis. In this chapter, we provide a detailed overview of the CTAs, with primary emphases on their structure, bioactivity, and total synthesis.