In this study, hydrocalumite-like Ca2Al-NO3− layered double hydroxides (Ca-Al LDHs) with different microstructures were synthesized. The crystalline properties, structure composition, morphology and particle size distribution of the Ca-Al LDH (CAL) samples were illustrated. To obtain the chloride uptake performances of CAL, the influences of contact time, initial concentration of Cl−, pH of reaction solution and coexistence anions on the chloride uptake were examined systematically. Compared to the CAL samples obtained at a higher aging temperature, CAL synthesized at 60 °C demonstrated the minimum average particle size (6.148 μm) and the best Cl− adsorption capacity (211.324 mg/g). Based on the test results, the main adsorption mechanism of chloride ion on CAL was recognized as an interlayer anion exchanging reaction other than the dissolution-precipitate mode. With the increase in the pH value of reaction solution from 7 to 13, it was found that the amount of chloride ion adsorbed by CAL increased slightly, and the solution could remain at relatively high pH value even after the adsorption. The presence of CO32− and SO42− reduced the adsorption capacity of CAL dramatically as compared with OH− due to the destruction of layered structure and the formation of precipitates (CaCO3 or CaSO4). The interference sequence of the investigated anions on the chloride uptake of CAL was SO42−, CO32− and OH−, and the order of interlayer anionic affinity was Cl− > OH− > NO3−. The results illustrated that the synthesized CAL could be used as a promising chloride ion adsorbent for the corrosion inhibition of reinforcement embedded cement-based materials.