Trifluoromethylated building blocks and intermediates are in exceptionally high demand for the synthesis of agrochemicals, pharmaceuticals, and specialty materials. Readily available, nontoxic and ozone-friendly fluoroform (CHF3, trifluoromethane, HFC-23), a side-product of Teflon manufacturing and a potent greenhouse gas, would be by far the best CF3 source for a variety of trifluoromethylation reactions. Chemoselective activation of fluoroform, however, is highly challenging. This article provides an overview of synthetic methods employing fluoroform with emphasis on new trends and most recent, promising developments in the area.