A porosity-controllable Si-based composite electrode was fabricated in the present study. Poly(methyl methacrylate) (PMMA), which possesses the unique thermal property of unzipping, was utilized as a pore-forming agent during electrode fabrication. PMMA-treated electrodes presented relatively low volume expansion and little deformation during lithiation. The cyclic dilation behavior of PMMA-treated electrodes was investigated by applying an in situ electrochemical dilatometric method, and enhanced dimensional reversibility during cycling was observed. The dilation behavior was closely related to the electrochemical performance, and PMMA-treated electrodes exhibited improved capacity retention and low impedance change during cycling. The newly generated pores in the PMMA-treated electrode can accommodate the volumetric expansion of Si-based active materials, which suppresses electrode deformation and the breakdown of the electrical network. The porosity plays an important role in Si-based electrodes. Thus, controlling the porosity through PMMA-treatment can be an effective way for the application of Si-based composite electrodes for advanced lithium-ion batteries.