Advanced oxidative processes (AOP) have been consolidated as an efficient treatment technique to degrade persistent contaminants. In addition to them, biosorption also emerges as a technique capable of removing both pollutants and intermediate products generated by other treatments such as AOP. Thus, this work evaluated the degradation and removal of the mixture of dyes Direct Red 23 and Direct Red 227 in aqueous solution (50 mg·L of each). Preliminary tests showed that the photo-Fenton system under sunlight radiation was the most efficient, reaching a degradation ≥93%. For the adsorptive process using chicken eggshell, preliminary tests indicated that the ideal dosage of adsorbent was 8.0 g·L. For this process, a factorial design indicated the best working conditions, which demonstrated from the system adjusted well to the Elovich (kinetic) model and to the Freundlich and Sips models (equilibrium). When associating the two processes, AOP followed by adsorption achieved a total degradation/removal of ≈98% (for all λ) in a time of 60 min. Thus, the feasibility of the combined treatment is indicated.