The effective functionalization of CH bond in methane, the main hydrocarbon component in Earth's crust and the most real source of energy for mankind in the nearest observable future, is undoubtedly can be regarded nowadays as one of the most important scientific and technological tasks. However, the usual practice of considering catalytic and gas-phase processes as independent technological branches seriously restricts the possibilities for a deeper understanding and technological optimization of real processes. The development of more effective technologies to convert methane and other gas-phase hydrocarbons into more valuable and demanded chemicals needs a complex approach based on the combined heterogeneous–homogeneous chemistry of these processes. A number of examples are used to illustrate the interconnection between heterogeneous catalytic and gas-phase processes in oxidative functionalization of methane. A number of potential possibilities for the optimization of the real heterogeneous–homogeneous chemistry of these processes are discussed.