We present the first example of water soluble complexes of carotenoids. The stability and reactivity of carotenoids in the complexes with natural polysaccharide arabinogalactan were investigated by different physicochemical techniques: optical absorption, HPLC, and pulsed EPR spectroscopy. Compared to pure carotenoids, polysaccharide complexes of carotenoids showed enhanced photostability by a factor of 10 in water solutions. A significant decrease by a factor of 20 in the reactivity toward metal ions (Fe3+) and reactive oxygen species in solution was detected. On the other hand, the yield and stability of carotenoid radical cations photoproduced on titanium dioxide (TiO2) were greatly increased. EPR measurements demonstrated efficient charge separation on complex-modified TiO2 nanoparticles (7 nm). Canthaxanthin radical cations are stable for similar to 10 days at room temperature in this system. The results are important for a variety of carotenoid applications, in the design of artificial light-harvesting, photoredox, and catalytic devices.