Upon slow warming of previously photolyzed matrix samples of OCS/Ar, CS2/Ar, OCS/Kr, and OCS/SF6 (M/R = 100), the B (B″)→X chemiluminescence of S2 is observed, as reported earlier. In addition, two new progressions were recorded, a weak progression between 5580-6890 Å and a stronger one between 6680-8750 Å. With OC34S, the 6680-8750 Å progression displayed isotopic shifts that allow deduction of ν00 = 15750±10 cm-1, ω″e = 699 ± 5 cm-1, and ωexe″ = 2.6 ± 1 cm-1. Similarly, the weaker 5580-6890 Å progression corresponds to ν00 = 20870 ± 30 cm-1, ω″ e = 724 ± 6 cm-1, and ωex″ e = 2.9 ± 1 cm-1, with a less favored, alternative vibrational assignment that gives ν00 = 21600 ± 30 cm -1, ω″e = 731 ± 6 cm-1, and ωex″e = 2.9 ± 1 cm-1. These spectroscopic parameters point to assignments of the c 1Σ g-→a 1Δg and A′ 3Δu → X 3Σg - transitions of S2 for the 6680-8750 Å and 5580-6890 Å emissions, respectively. These are the first observations of these transitions of diatomic sulfur, and one of them provides the first direct spectroscopic information illustrating that the c 1Σ u-l state (T0 = 20250 ± 200 cm -1) actually lies lower than the A 3Σ u+ and A′ 3Δu states, as is the case for O2.