The destabilization of halogenated disinfection-by-product (DBP) precursors by coagulation are mostly subjected to Al speciation of polyaluminum chloride (PACl) and the fraction of dissolved organic matter (DOM), which significantly affect the minimization of halogenated DBP precursors, such as trihalomethane (THM) and haloacetic acids (HAA), in post-chlorination. In this study, the destabilization of DOM in the solution of humic acid (HA) with and without algogenic organic matter (AOM) using two PACl coagulants with different Al speciation was investigated, along with the identification of optical properties for DOM fractions. Additionally, total THM and HAA formation potential of the supernatant before and after coagulation-sedimentation were determined. The results showed that high polymeric Al-containing PACl (PACl-H, 66% Al13) outcompetes in destabilizing HA than commercial PACl (PACl-C, 29% Al13, 32% Al(OH)3). However, the removal of DOM in HA/AOM mixture by both PACl coagulants are significantly suppressed with greater removal of humic-like and fulvic-like substances than aromatic protein-like substances after coagulation-sedimentation, where PACl-C shows superiority in the removal of hydrophobic and hydrophilic substances with MW around 1 kDa than PACl-H. In the absence of AOM, total THM and HAA formation potential were effectively reduced for HA coagulation by both PACl, but vice versa with the presence of AOM, especially for cellular organic matter (COM). Minimization of halogenated DPB precursors by coagulation are predominated by destabilized hydrophilic molecule fractions with Al hydrates. It is concluded that PACl-H favors charge neutralization to destabilize total carbonaceous DBP (C-DBP) precursors in HA or HA/AOM mixture and the corresponding C-DBP formation potential is lower compared to PACl-C that predominates adsorption and co-precipitation in destabilizing C-DBP precursors.