This study reports the first synthesis of a new type of ether-polyalphaolefin (DVE-PAO) base oil via free radical bulk copolymerization using triethylene glycol divinyl ether (DVE-3) and α-olefin in drip-feed mode. The characteristic structure of DVE-PAO was characterized by Fourier Transform Infrared Spectroscopy (FTIR) and Nuclear Magnetic Resonance Spectroscopy (NMR). The relative molecular weight and molecular weight distribution of DVE-PAO were determined using gel permeation chromatography (GPC). Structurally, it is a new type of base oil that integrates both polyalkylene glycol (PAG) and polyalphaolefin (PAO) structural units. The research shows that the viscosity of DVE-PAO base oil, the conversion rate of α-olefin, and the pour point of the copolymer increase with rising copolymerization temperature. Additionally, results from the rotating oxygen bomb test indicate that the oxidation stability of DVE-PAO also improves with increasing viscosity. Based on the principles of free radical copolymerization, this study provides a preliminary elucidation of the copolymerization patterns between the aforementioned double-ended vinyl ethers and α-olefins. Furthermore, the DVE-PAO base oil exhibits excellent miscibility with both mineral oils and polyalphaolefin (PAO) base oils. As a result, this ether-based polyalphaolefin is expected to find broad applications in the field of lubricants.