A fine crystalline ammonium tungstophosphate (AWP) exchanger with high selectivity toward Cs+ was encapsulated in biopolymer matrices (calcium alginate, CaALG). The characterization of the AWP-CaALG microcapsule was examined using SEM/WDS, IR and DTA/TG analyses, and the selective separation and recovery of 137Cs were examined by the batch and column methods using simulated and real high-level liquid waste (HLLW). The free energy (ΔG0) of the ion exchange (NH4+ ↔ Cs+) for fine AWP crystals was determined at-13.2 kJ/mol, indicating the high selectivity of AWP towards Cs+. Spherical and elastic AWP-CaALG microcapsules (∼700 μm in diameter) were obtained and fine AWP crystals were uniformly immobilized in alginate matrices. Relatively large Kd values of Cs+ above 105 cm3/g were obtained in the presence of 10-3∼1 M Ca(NO3)2, resulting in a separation factor of Cs/Rb exceeding 102. The irradiated samples (60Co, 17.6 kGy) also exhibited large Kd values exceeding 10 5 cm3/g in the presence of 2.5 M HNO3. The Kd values in the presence of 0.1∼9 M HNO3 for 67 elements were determined and the order of Kd value was Cs+ ≫ Rb+> Ag+. The breakthrough curve of Cs+ had an S-shaped profile, and the breakpoint increased with decreasing flow rate; the breakpoint and breakthrough capacity at a flow rate of 0.35 cm3/min for the column (0.7 g AWP-CaALG) were estimated at 25.2 cm3 and 0.068 mmol/g, respectively. Good breakthrough and elution properties were retained even after thrice-repeated runs. The uptake (%) of Cs+ in simulated HLLW (28 metal components-1.92 M HNO3, SW-11, JAEA) was estimated at 97%, and the distribution of Cs+ and Zr/Ru into the AWP and alginate phases, respectively, were observed by WDS analysis. Further, the selective uptake of 137Cs exceeding 99% was confirmed by using real HLLW (FBR "JOYO", JAEA). The AWP-CaALG microcapsules are thus effective for the selective separation and recovery of Cs+ from HLLWs.