The invention discloses a Ni-Cu-La-B quaternary alloy plating solution. The Ni-Cu-La-B quaternary alloy plating solution comprises the following components: 20-40g / L of nickel chloride, 10-20g / L of copper sulfate, 0.5-10 g / L of lanthanum sulfate, 0.5-3 g / L of sodium borohydride, 40-50g / L of potassium sodium tartrate, 15-30g / L of ethylenediamine and 35-60g / L of sodium hydroxide. A method for chemically plating the glass fibers by using the Ni-Cu-La-B quaternary alloy plating solution comprises the following steps: using sodium borohydride as a reducing agent, adding the water-soluble lanthanum sulfate, and chemically plating the glass fibers by using the Ni-Cu-La-B quaternary alloy plating solution under the conditions of strong base and low temperature; plating layers are Ni-Cu-La-B alloy plating layers, wherein the content of boron is low (only about 0.5-5wt%), the content of nickel in the plating layers is high; the plating layers have good bonding force, electrical conductivity and wear resistance. Through observation with microscopes, the plating layers of the Ni-Cu-La-B quaternary alloy plated glass fibers prepared by using the method are compact; testing with an X-ray energy dispersive spectrometer shows that the surface chemistry components of the Ni-Cu-La-B quaternary alloy plated glass fibers contain 15-50wt% of Ni, 2-15wt% of Cu, 0.5-5wt% of La and 0.5-5wt% of B. The electric conducting glass fibers can be applied to the special fields of electromagnetic wave shielding, microwave absorption, invisibility, anti-static electricity and the like.