Abstract An efficient cathodic electrodeposition method is developed for coating Co‐based metal‐organic frameworks (Co‐MOF) on carbon fiber cloth (CFC), a widely used substrate in energy fields. The use of a highly active Co metal surface enables nucleation and growth of Co‐MOF in 3D rodlike crystal bundles. When used as a binder‐free electrode (Co‐MOF/CFC) for supercapacitors, it shows a high areal capacitance of 1784 mF cm−2 at 1 mA cm−2, good cycling stability and excellent rate capability. The assembled asymmetric all‐solid‐state supercapacitor device (Co‐MOF/CFC//AC) delivers a high energy density and power density. This work may open up an effective approach to realize the electrosynthesis of MOF films, promoting use in energy storage and conversion fields.