Photocatalysis is a promising process for decomposing harmful organic pollutants in water. In this study, solar/photocatalytic degradation of two model azo dyes, i.e., methylene blue (MB) and methyl red (MR), in water usinga nanostructured chitosan-modified nickel magnetite (CS-NM) bio-composite was investigated. The CS-NM bio-composite was synthesized through a co-precipitation method and characterized by Fourier transform infrared (FTIR), scanning electron microscopy (SEM), energy dispersive X-ray (EDX), thermogravimetry (TGA), and UV-Vis spectroscopy. FTIR analysis showed the uniform incorporation and conjugation of nickel magnetite (NM) into the chitosan (CS) polymer matrix. SEM showed that the average particle size was 0.5 μm. The TGA results revealed the good thermal stability of the prepared bio-composite at 300 °C. The point of zero charge was calculated as 7.5. The effect of water quality and process parameters, such as concentration of dyes, catalyst dose, solution pH, and temperatures, was investigated, for application purposes. The solar/CS-NM photocatalysis resulted in 99 and 96% degradation of individual MB and MR (C0 = 50 ppm), respectively, in 90 min. The degradation of MB and MR by solar/CS-NM photocatalysis followed pseudo-first-order kinetics, with observed rate constants (k) of 0.077 and 0.072 min−1, respectively. The CS-NM photocatalyst showed high recyclability, represented by only a 4–6% loss in the photocatalytic efficiency, after four cycles. The results showed that solar/CS-NM photocatalysis is an efficient technique for degrading recalcitrant organic pollutants, such as azo dyes, in water environments.