Carbon nanotubes (CNTs) have been widely used as electrode materials for electrochemical energy storage devices (e.g., supercapacitors) due to their excellent chemical and physical properties. However, conventional approaches (e.g., electron-beam vapor deposition and atomic layer deposition) to fabricate catalysts for the growth of CNTs are complex and demand high energy consumption. Herein, we report a facile method to synthesize catalysts derived from cobalt-containing zeolitic imidazolate frameworks (Co-ZIFs), which is exploited to in situ construct the three-dimensional (3D) CNT hybrid materials for all-solid-state supercapacitors. In brief, Co-ZIFs with a controllable structure is first grown on the inner porous surface of carbon foams pyrolyzed from commercial melamine foams, followed by thermal annealing and chemical vapor deposition to grow CNTs, achieving 3D free-standing CNT-based hybrids. The well-distributed Co-ZIFs in the carbon foam enable the grown CNTs with uniform structures and morphologies. Using the fabricated CNT-based hybrid as electrodes, the assembled all-solid-state supercapacitors show a high specific capacitance of 19.4 mF cm-2 at a current density of 0.5 mA cm-2, which could be further optimized to as high as 871.8 mF cm-2 by incorporating the pseudocapacitive material of manganese dioxide in CNT-based hybrids. This study provides a facile solution approach to fabricate the catalyst for the growth of a CNT inner porous substrate; the resultant 3D free-standing hybrids could be used as efficient electrodes for high-performance energy storage devices beyond supercapacitors.