Direct C–H bond functionalization catalyzed by non-precious transition metals is an attractive strategy in synthetic chemistry. Compared with the precious metals rhodium, palladium, ruthenium, and iridium commonly used in this field, catalysis based on non-precious metals, especially the earth-abundant ones, is appealing due to the increasing demand for environmentally benign and sustainable chemical processes. Herein, developments in iron- and cobalt-catalyzed C(sp³)–H bond functionalization reactions are described, with an emphasis on their applications in organic synthesis, i.e., the synthesis of natural products and pharmaceuticals and/or their modification.