It has been an urgent need for developing a new bright long‐wave emitting phosphor to improve the color rendering index (CRI) of white light‐emitting diodes (WLEDs). Here, based on the concept of oxygen vacancy‐induced long‐wave emission by Bi3+ doping, we selected BaSrGa4O8 as the matrix, which has a low‐dimensional chain structure that can produce enough oxygen vacancies. After the introduction of Bi3+, orange emission was successfully achieved. To further improve the luminescence efficiency, the system of BaSrGa4O8:Bi3+,K+ was designed. Interestingly, although significant emission enhancement was obtained, the material showed reduced absorption with increased oxygen vacancies. More detailed experimental evidences confirm that oxygen vacancies can activate Bi3+ to achieve long‐wave emission. Our results provide a new way to design Bi3+‐based long‐wave emitting phosphors with low‐dimensional crystal structure. Finally, a WLED device containing BaSrGa4O8:Bi3+,K+ was fabricated and exhibited an enhanced CRI, which shows a promising application in WLEDs.