Addressing the inherent brittleness of cement to mitigate infrastructure failures stemming from cracking is imperative. To accomplish both early crack resistance and subsequent self-healing capabilities, a biomimetic microstructure composed of a sodium polyacrylate (CSPA) network interwoven with hydration products was developed. The calcium-enriched polymer network formed via in situ polymerization of sodium acrylate (ANa) can enhance the mechanical properties of cement and achieve efficient self-healing of cracks. The porous structure of sodium polyacrylate (PANa) formed in pore solution at room temperature to simulate cement hydration conditions was observed by scanning electron microscopy (SEM). Feature peaks found by Fourier transform infrared (FTIR) spectroscopy as well as confocal Raman microscopy (CRM) suggested that ANa was polymerized successfully. Notably, CSPA samples demonstrated a remarkable 104% increase in flexural strength, attributed to the efficient transmission and dissipation of external forces along the polymer network embedded within the cement matrix. Additionally, after a 28-day hydration, CSPA specimens exhibited enhanced compressive strength compared to blank cement samples. This enhancement stems from the formation of a uniform polymer network, which effectively decreased the porosity and densified the microstructure of cement. Moreover, this organic–inorganic hybrid structure contributes to efficient crack healing, as the calcium-rich polymer network binds calcium ions and promotes the generation of healing products. The healing products consist of calcium hydroxide (CH), CaCO₃ (aragonite), C-S-H (calcium–silicate–hydrate), and PANa.