Efficient top‐emission and transparent OLEDs with decomposable alkali compounds as the electron injection layer have been developed. The alkali compounds, such as alkali nitrides and carbonates, decomposed during vacuum thermal evaporation to liberate alkali metals. Therefore, inert metals such as Ag can be used as the rear cathode. Top‐emission device with Li3N/Ag cathode showed a turn on voltage of less than 3.0 V, a current efficiency of 8.3 cd/A and a brightness of more than 105 cd/m2 at 10 V. Our study shows that alkali/Ag cathode is an excellent candidate for transparent cathode in top emission or transparent devices.