LiMo3Se3 is a highly anisotropic solid comprised of a regular pattern of quasi-1-D wire-like structures. Solutions of LiMo3Se3 deposited on substrates and TEM grids reveal the presence of two-dimensional network morphologies. High resolution STEM imaging reveals that the junctions within these networks are not formed by discrete overlying LiMo3Se3 fibers or wires. Rather the junctions are continuous in that the wires are seamlessly interwoven from one bundle to the next. We investigated network formation by dynamic light scattering and AFM and demonstrate that the networks are not pre-existent in solution but rather form via self-assembly of nanoscale building blocks that is driven by solvent evaporation.