Besides tough kinetic issues in S cathodes, a poor S filling ratio, and a low compact density in films led by the overuse of porous hosts, conducting agents or other additives impede the further progress of Li−S cells. To overcome these constraints, we herein propose the rational design of robust NiO nanoframeworks to make high S filling and binder-free cathodes. Notably, such arrayed thick frameworks have an impressive spatial filling ability, showing a remarkable S filling ratio of 77.6%. To further optimize the cell behaviors, all of the arrayed NiO matrix surface is evenly paved by graphitic carbon shells, and the open-up architecture for S-filled frameworks is intactly encapsulated by functionalized nickel nitrate hydroxide layers. Thanks to subtle interfacial engineering and smart hybrid configurations, a high initial discharge capacity of over 1481 mAh g −1 and a longer-term cyclic lifespan are achieved at 0.1 C. Also, this optimized binder-free cathode leads to great improvements in Coulumbic efficiency, the S utilization ratio, and rate capabilities. Our work presents not only an appealing route to making high S filling and binder-free cathodes for Li−S cells but also insight for the smart design of integrated film electrodes for other electrochemical applications.