Laser photolysis at 193 urn of gaseous carbon disulfide into CS and S in the absence and excess of N-2 is controlled by two-photon-induced depletion of CS2 and affords chemical vapor deposition of (CS)(n) polymer and S-n. The proposed polymerization mechanism of CS is explained by an intermediacy Of C2S2 species. The (CS)(n) polymer contains S-centered radicals that are stable in air and withstand heating in a H-2 atmosphere. Its structure is contributed by >C=S, >C=C<, S2C=CS2, -C-(C=S)-S-, -S-(C=S)-S-, and C-S-S-C configurations whose relative extent depends on irradiation conditions: more C=S bonds (and fewer C-S bonds) are formed at higher CS2 pressure, in the excess of N-2 and with lower laser fluences. The extent of the S2C=CS2 units decreases, and that of >C=C< units increases, upon mild polymer heating. The polymer deposited in the absence of N-2 consists of unique 100-200 nm sized hollow spheres.