Poly(p‐phenylene sulfide) (PPS) is a melt‐ and solution‐processible polymer which on treatment with AsF5 forms a blue‐black material with a conductivity of 1–10 Ω−1 cm−1. Thermopower measurements indicate that the resulting polymer is p type, consistent with partial oxidation of the PPS by the AsF5. The rate and extent of this doping process prove to be particularly sensitive to the degree of crystallinity of the starting polymer. There is also evidence of crosslinking of the polymer chains during the reaction with AsF5. The details of both the chemistry and physics of the doping of PPS and several of its derivatives are presented.