Silicon anodes are considered to have great prospects for use in batteries; however, many of their defects still need to be improved. The preparation of hybrid materials based on porous carbon is one of the effective ways to alleviate the adverse impact resulting from the volume change and the inferior electronic conductivity of a silicon electrode. Herein, a chain-like carbon cluster structure is prepared, in which MOF-derived porous carbon acts as a shell structure to integrally encapsulate Si nanoparticles, and CNTs play a role in connecting carbon shells. Based on the exclusive structure, the carbon shell can accommodate the volume expansion more effectively, and CNTs can improve the overall stability and conductivity. The resulting composite reveals excellent rate capacity and enhanced cycling stability; in particular, a capacity of 732 mA·h·g−1 at 2 A·g−1 is achieved with a reservation rate of 72.3% after cycling 100 times at 1 A·g−1.