We proposed an efficient method toward the synthesis of higher tungsten boride WB5-x in the vacuumless direct current atmospheric arc discharge plasma. The crystal structure of the synthesized samples of boron-rich tungsten boride was determined using computational techniques, showing a two-phase system. The ab initio calculations of the energies of various structures with similar X-ray diffraction (XRD) patterns allowed us to determine the composition of the formed higher tungsten boride. We determined the optimal parameters of synthesis to obtain samples with 61.5% WB5-x by volume. The transmission electron microscopy measurements showed that 90% of the particles have sizes of up to 100 nm, whereas the rest of them may have sizes from 125 to 225 nm. Our study shows the possibility of using the proposed vacuumless method as an efficient and inexpensive way to synthesize superhard WB5-x without employing resource-consuming vacuum techniques.