Preliminary results on the synthesis and characterization of anisotropic networks, oriented on a macroscopic scale, are reported. Fiber samples of segmented thermotropic Liquid-crystalline polymers bearing the oxypentenyl lateral substituent have been crosslinked via thermally activated radical reaction. This was made possible by immersion of fiber samples in dichloromethane containing t-butylperoxybenzoate as activating agent, thus allowing its diffusion in the samples. Subsequent annealing at 145 degrees C brings us to an anisotropic network with no loss of the original orientation. A mesophase is stabilized and no structural modification is observed by heating samples from room temperature up to 400 degrees C, where thermal decomposition takes place. Crosslinked fibers exhibit good tensile properties, at both room temperature and at 150 degrees C.