We compare and contrast the results of transient absorption measurements on three members of the poly(arylenevinylene) family: poly(p-phenylenevinylene), PPV; poly(2,5-dimethoxy-p-phenylene vinylene), PDMeOPV; and poly(2,5-thienylenevinylene), PTV. In PTV we observe a rapid decay of the transient signal, which we related to the low efficiency for luminescence. We observe a much longer-lived transient absorption in PPV, which we consider to arise from singlet and triplet polaron-excitons. The results in PDMeOPV suggest the possibility that bipolarons may also contribute to the transient absorption. © 1993.