Cross-coupling reactions leading to carbon–heteroatom bonds yield compounds that attract substantial interest due to their role as structural units in many synthetic protocols for bioactive and natural products. Therefore, many research works aim at the improvement of heterogeneous catalytic protocols. We have studied the use of magnetite nanoparticles and solid base compounds in organic synthetic reactions in carbon–heteroatom bond formation because they can be flocculated and dispersed, and reversibly controlled by applying a magnetic field. In this work, we have developed an efficient and simple synthetic approach for the C–O/C–N cross-coupling reaction under ligandfree conditions by using CuI as a catalyst and KF/Fe3O4 as a base. We performed the nucleophilic aromatic substitution of electron-deficient aryl halides and phenols. It was found that both the solvent nature and the base have a profound influence on the reaction process. This approach affords good to excellent yields of arylated products. KF/Fe3O4 displayed convenient magnetic properties and could be easily separated from the reaction using a magnet and recycled several times without significant loss of catalytic activity. This method has been successfully investigated for the Ullmann coupling reaction.