Transitional metal chalcogenides like WS2 play a significant role as cocatalysts in activating PMS (peroxymonosulfate) due to their high reductivity. Three WS2 samples with different morphologies, specific surface areas, and 1 T phase contents were prepared in this study. Characterizations by SEM, TEM, BET, XRD, Raman, XPS, and catalytic degradation experiments confirmed that the a-WS2 sample exhibited the richest morphology, the largest specific surface area, the highest 1 T phase content, and the best cocatalytic performance. The a-WS2/Fe(II)/PMS system efficiently degraded 20 mg/L phenol within 15 minutes and was also effective in degrading pollutants like RhB (Rhodamine B) and OFX (Ofloxacin). Characterization predicted the degradation pathway of phenol and revealed 10 intermediate products. The degradation mechanism indicated that the presence of WS2 accelerated the conversion of Fe(III) to Fe(II), thereby further promoting the activation of PMS. ·SO4−, ·OH, and ·O2− were identified as the main active radicals in this system. a-WS2 exhibits characteristics such as high catalytic performance, good stability, high recyclability, and a low ion leaching rate, and it generates sulfur vacancies during use. This system shows promising prospects in the treatment of high-concentration organic wastewater.