Polysaccharides play a crucial role in virtually all living systems. They also represent the biocompatible and fully sustainable component of a variety of nanoparticles, which are of increasing interest in biomedicine, food processing, cosmetics, and structural reinforcement of polymeric materials. The computational modeling of complex polysaccharide phases will assist in understanding the properties and behavior of all these systems. In this paper, structural, bonding, and mechanical properties of 10 wt % cellulose-callose hydrogels (β-glucans coexisting in plant cell walls) were investigated by atomistic simulations. Systems of this kind have recently been introduced in experiments revealing unexpected interactions between the polysaccharides. Starting from initial configurations inspired by X-ray diffraction data, atomistic models made of ∼1.6 × 106 atoms provide a qualitatively consistent view of these hydrogels, displaying stability, homogeneity, connectivity, and elastic properties beyond those of a liquid suspension. The simulation shows that the relatively homogeneous distribution of saccharide nanofibers and chains in water is not due to the solubility of cellulose and callose, but to the formation of a number of cross-links among the various sample components. The broad distribution of strength and elasticity among the links implies a degree of anharmonicity and irreversible deformation already evident at low external load. Besides the qualitative agreement with experimental observations, the simulation results display also quantitative disagreements in the estimation of elastic coefficients, such as the Young's modulus, that require further investigation. Complementary simulations of dense cellulose-callose mixtures (no hydrogels) highlight the role of callose in smoothing the contact surface of different nanofibers forming larger bundles. Cellulose-callose structures in these systems displayed an enhanced water uptake and delayed dye release when compared to cellulose alone, highlighting potential new applications as drug delivery scaffolds. The simulation trajectories provide a tuning and testing ground for the development of coarse-grained models that are required for the large scale investigation of mechanical properties of cellulose and callose mixtures in a watery environment.