Ruthenium removal from complex solutions (highly saline effluents, seawater) is a critical challenge. Herein, the sorption capacity of chitosan/SiO2 composite beads (Ch-Si) for ruthenium nitrosyl is increased three-fold after phosphoramidate grafting (DPA-Ch-Si, 1.6 mmol Ru g−1) at pH 5. Uptake kinetics and sorption isotherms are compared at pH0: 3, 5 and 10; playing with the mode of agitation (mechanical, MA, vs. ultrasonic treatment, UT). The sorbent maintains good sorption capacities at pH 3 and 10. Uptake kinetics modeled by pseudo-first order rate equation is boosted by functionalization. For Ch-Si, sorption isotherms are modeled by the Langmuir or Sips equations (depending on the pH), while for DPA-Ch-Si the best fits depend on pH, temperature and mode of agitation. Ruthenium sorption is spontaneous and endothermic for the two sorbents. For DPA-Ch-Si, the sorption capacity increases from 1.62 to 1.70 mmol Ru g−1 to 2.23–2.32 mmol Ru g−1 (T increasing from 21 to 50 °C). Nitric acid solution (0.3 M) reveals highly efficient for back extraction; ruthenium is completely released in <15 min. The functionalized sorbent can be reused for a minimum of 10 cycles, with limited loss in performance. Phosphoramidation improves sorption selectivity for the treatment of equimolar multicomponent solutions (Na, Ca, Mg, Fe, Al, U, and Nd). The effect of pH on sorption selectivity is evaluated in simple multi-metal solutions and complex environment. In seawater, the selective recovery of ruthenium is favored at pH close to 10. These tests confirm the promising perspectives offered for ruthenium removal from complex environments. Physicochemical characterizations of the sorbent (and their modes of interaction with ruthenium nitrosyl) included SEM, BET, TGA, FTIR, XPS, and elemental analyses.