The morphological and optical properties of microstructured silicon substrates (M‐Si), and inverted top‐emitting organic light‐emitting diodes (ITOLEDs) based on the M‐Si/Ti/TiN/Al composite electrodes were studied. The developed M‐Si/Ti/TiN/Al composite electrodes functioned well in improving the performance of red, green, and blue ITOLED. The Al thin film deposited on TiN silicon substrate could significantly improve the reflectivity of the electrode, and the microstructured substrate could further increase the reflective path for lights inside OLEDs. Meanwhile, by adopting a light output‐coupling layer on top of the device and using the localized surface plasmon resonance effect of the top‐emitting structure, the angle‐dependent effect of ITOLEDs based on the composite electrodes was reduced. Through employing the M‐Si/Ti/TiN/Al composite electrodes, all the red, green, and blue OLEDs achieved an improved performance, and the red OLED showed the best performance enhancement, with the luminance of 26247 cd/m2, maximum current efficient of 30.7 cd/A, and maximum external quantum efficiency of 17.4%. This provides a new strategy to achieve highly efficient ITOLEDs.This article is protected by copyright. All rights reserved.