As an important preparation method of Inorganic Polymer Flocculants (IPFs) with all-round performance, the use of enhanced reactions of modification for Polyaluminum Chlorides (PAC) is a trend of application. In this paper, auctorial-made multicore oligomers as a complexing agent, polysilicate as a crosslinking agent and polyacrylamide as a compounding agent are respectively used to enhance PAC and prepared three kinds of IPFs, named CO-PAC, CR-PAC and PAM-PAC. The Fourier Transform Infrared spectra (FTIR) of the three flocculants show that there have been found new chemical bonds beyond Al-OH in their structures, and each characteristic band of primary group in PAC has a band shift to a lower frequency due to its structural aberration. These evidences suggested that enhanced reactions of modification for PAC are not at all a simple process of physical mix, but a chemical reaction to form other structural characteristics of inorganic polymers. The excellent coagulation behavior of these new flocculants depends mainly on the chemical actions, but there are a little physical effects between the modifiers and PAC.