The prevalence of naphthalene compounds in biologically active natural products, organic ligands and approved drugs has motivated investigators to develop efficient strategies for their selective synthesis. C-H functionalization of naphthalene has been frequently deployed, but mainly involves two-component reactions, while multiple-component C-H functionalization for the synthesis of naphthalene compounds has thus far proven elusive. Herein, we disclose a versatile three-component protocol for the modular synthesis of multifunctional naphthalenes from readily available simple naphthalenes, olefins and alkyl bromides P(iii)-assisted ruthenium-catalyzed remote C-H functionalization. This protocol not only tolerates various functional groups, but can be applied to many natural product and drug derivatives, and can involve a three-component reaction with two different bioactive molecules. Mechanism studies indicated that the utilization of tertiary phosphines as auxiliary groups is the key to achieving the three-component free-radical reaction.