The cationic organic polymers used to enhance thickening and dewatering processes are potential sources of strong odors. These polymers vary in chemical structure, and some may be more susceptible to biotic or abiotic degradation than others. The product organic amines will be volatilized most noticeably at high pH, as in lime addition. These possibilities were examined using several structural types of polymers combined with anaerobically digested sludge. Two commonly used polymers gave significant production of trimethylamine (TMA), which was released upon lime addition. Their structures were correlated with reactions that yield TMA. An initial ester hydrolysis step appears to be biologically mediated, but subsequent steps can occur due to alkaline conditions. An alternative cationic polymer structure did not generate TMA but required a much higher dose to effect sufficient conditioning of the sludge. The acrylamide-based polymers were shown to be the predominant source of TMA in limed sludges.