We describe the formation and morphology of complex, ordered polysaccharide-based structures by combining the holographic method and a self-assembly. We use dichromated polysaccharide as holographic material. Multilayer structures were fabricated as a volume Bragg reflection grating recorded with the single-frequency, diode pumped Nd-YAG laser, at 532 nm. Inside the holographic volume Bragg layers, upon phase separation, polysaccharide is self-assembled into spheres with typical dimensions of 30 nm and 70 nm. Field emission gun scanning electron microscope (FEGSEM) images confirmed the morphology of these structures.