Cesium azide (CsN3) is employed as a novel n-dopant because of its air stability and low deposition temperature. CsN3 is easily co-deposited with the electron transporting materials in an organic molecular beam deposition chamber so that it works well as an n-dopant in the electron transport layer because its evaporation temperature is similar to that of common organic materials. The driving voltage of the p-i-n device with the CsN3-doped n-type layer and a MoO3-doped p-type layer is greatly reduced, and this device exhibits a very high power efficiency (57 lm W−1). Additionally, an n-doping mechanism study reveals that CsN3 was decomposed into Cs and N2 during the evaporation. The charge injection mechanism was investigated using transient electroluminescence and capacitance–voltage measurements. A very highly efficient tandem organic light-emitting diodes (OLED; 84 cd A−1) is also created using an n–p junction that is composed of the CsN3-doped n-type organic layer/MoO3 p-type inorganic layer as the interconnecting unit. This work demonstrates that an air-stable and low-temperature-evaporable inorganic n-dopant can very effectively enhance the device performance in p-i-n and tandem OLEDs, as well as simplify the material handling for the vacuum deposition process.