Condition-controlled switchable and divergent transformations of cost-effective 2-bromo-3,3,3-trifluoropropene (BTP) and aldehydes were realized using a decatungstate (TBADT)-photocatalyzed strategy. The hydroacylated products, i.e., β,β-Br,CF 3 -ketones, can be applied as highly functionalized synthetic building blocks for the selective synthesis of ( Z / E )-β-CF 3 -enones. Utilizing this methodology, a broad range of commercially available aromatic and aliphatic aldehydes as well as numerous complex aldehydes, such as lily aldehyde, cyclamen aldehyde, citronellal, vanillin, and aldehydes containing bioactive moieties, including ibuprofen, gemfibrozil, naproxen, flurbiprofen, oleic acid, and aspirin, may be proficiently employed in this transformative process.