In this paper, the mechanism of photo-carrier generation in polymer with conjugatedtriple bond-poly(bis(p-toluene sulphonate)ester of 2,4-hexadiyne-l,6-diole)(PDA-TS) isstudied. We infer that photo-carriers are generated by dissociation electron-hole pairs which were produced by photo-excitation initially, and by thermalization of polaron-excitons which were formed through relaxation, respectively, The formation and characters of triple exciton in PDA-TS are analyzed in detail.