In this study, guar gum fibers were obtained by wet spinning, in which epichlorohydrin (ECH) and calcium chloride (CaCl2) were used as the cross-linking agent and metal complexing agent, respectively. The fibers' chemical structure, morphology, crystallinity, and thermal and mechanical properties were analyzed by Fourier infrared spectroscopy, scanning electron microscopy, and so forth. The results showed that ECH reacted with guar gum and formed ether bonds. Meanwhile, ECH can effectively increase the number of cross-linking points and improve the mechanical properties of the fibers. When the ECH content was 12% (w/w), the breaking strength could reach 2.4 cN/dtex. The conductivity of MC-GG fibers varied with the relative humidity and could reach 2.845 × 10-2 S/cm at maximum. Meanwhile, the contact angle of MC-GG fibers was 33°, indicating that the fibers had good hydrophilicity and humidity response ability and had excellent potential in the field of smart fabrics.