The invention discloses an environmentally-friendly insulating gas combined production technology and an industrial production device thereof. The combined production technology comprises the following steps: 1, carrying out a contact reaction on oxygen and HFP in a first fixed bed reactor under a catalyst condition or a catalyst-free condition; 2, mixing a gas product flowing out of the first fixed bed reactor with the HFP, allowing the gas product and the HFP to enter a second fixed bed reactor, and carrying out a contact reaction in the second fixed bed reactor under the action of a catalyst; and 3, carrying out separation on the effluent of the second fixed bed reactor to prepare a C5 product and a C4 product. Combined production of two novel environmentally-friendly insulating gases is realized from cheap raw materials comprising perfluoropropylene and oxygen at an atom economy of 80-90%, so the production cost is greatly reduced, and the discharge of three wastes in the production process is reduced.