To control drugs in vivo, new approaches are needed. Considerable progress has been made towards the applications of fluorine (¹⁹F) in pharmacotherapy in this regard. To date, many authors have showed that by using ¹⁹F labelled drugs and non-invasive magnetic resonance imaging (MRI) techniques together, drug biodistribution can be tracked. This review presents methods for ¹⁹F incorporation into pharmaceuticals by forming C–F bonds and drug fluorine oil-water emulsions. Inadequate drug delivery is a major cause of drug resistance, which can be improved using approaches discussed herein aided by ¹⁹F MRI.