Anaerobic digestion with thermal hydrolysis pretreatment (THP), also called advanced anaerobic digestion (AAD), is a mainstream technology for sludge treatment. AAD changes sludge, it can degrade extracellular polymeric substances (EPS), release EPS from the sludge, and alter the particle size distribution. We synthesized PFS-PDMDAAC from the inorganic coagulant polyferric sulfate (PFS) and the organic coagulant polymer polydimethyldiallylammonium chloride (PDMDAAC) in various PFS:PDMDAAC weight ratios. We investigated the effects of PFS-PDMDAAC pretreatment on AAD sludge dewaterability, and developed an explanation for them. Capillary suction time (CST) was used as a measure of sludge dewaterability. Dissolved organic matter, the three-dimensional excitation emission matrix, particle size (d0.5), zeta potential, and sludge microstructure were observed in order to explain changes in sludge dewaterability that resulted from different compositions and dosages of coagulants. Treatment with PFS alone gave no significant improvement in sludge dewaterability. PDMDAAC used alone greatly improved sludge dewaterability. Synthesized PFS-PDMDAAC which had a relatively high proportion of PDMDAAC by weight performed similarly to PDMDAAC. PFS-PDMDAAC synthesized in the ratio (PDF:PDMDAAC) 1:5 by weight provided good dewaterability. The dosage can be reduced by 16.7% of the dosage for conditioning by PDMDAAC alone.