An unprecedented cross-coupling reaction of alkyl carbagermatranes with bromofluoroolefins to deliver dialkyl-substituted monofluoroalkenes was achieved. This cross-coupling reaction was performed under base/additive-free conditions with excellent functional group tolerance, therefore offering an opportunity for challenging dialkyl-substituted monofluoroalkenes. The preparation of bioactive agent analogues including an antitubercular agent mimic and a COX-2 inhibitor analogue and the late-stage fluoroalkenylation of drug-molecule derivatives proved the utility of this strategy.