Copper iodide (CuI) nanoparticles/boron nitride nanosheets (BNNSs) were prepared via an ultrasonication method and subsequently characterized. For the first time, these newly synthesized CuI/BNNS supports were used as heterogeneous catalysts for C-H difluoromethylation reactions, including the synthesis of heteroarenes and terminal alkynes. The versatility of the catalyst was demonstrated for the synthesis of diverse substituted difluoromethylated heteroarenes and terminal alkynes from electron-deficient and electron-rich groups, resulting in moderate to high yields (up to 91%). The reaction was carried out in a greener medium (cyrene instead of dimethylformamide and N-methyl-2-pyrrolidone) at room temperature using (difluoromethyl)trimethylsilane and 9,10-phenanthraquinone in the presence of the CuI/BNNS catalyst containing similar to 3 wt% Cu and I. Notably, its activity was found to provide higher yield, shorter reaction time, and fewer usage of the catalyst, compared with commercial CuI catalysts. In addition, the CuI/BNNS catalyst could be easily recovered and recycled up to five times, with only a slight decrease (3%) in its catalytic activity, providing attractive features for chemical engineers to use this catalyst for the large-industrial scale synthesis of organic bioactive compounds involving C-H difluoromethylation reactions.