Series of anionic flocculants with outstanding flocculation performance, poly(acrylic acid-co-acrylamide)/diatomite composite flocculants (PAAD) were successfully prepared through aqueous solution copolymerization and applied to flocculate from oil-field fracturing waste-water. The structure of PAAD was characterized by Fourier transform infra-red spectroscopy , 13C nuclear magnetic resonance and X-ray diffraction tests, and its properties were systematically evaluated by viscometer, thermogravimetry analysis and flocculation measurements. Furthermore, the influences of various reaction parameters on the apparent viscosity of flocculant solution were studied, and the optimum synthesis condition was determined. The novel composite flocculants exhibited outstanding flocculation properties. Specifically, the dosage of composite flocculants that could make the transmittance of treated wastewater exceed 90% was only approximately 12–35 ppm, which was far lower than that of conventional flocculants. Meanwhile, the settling time was lower than 5 s, which was similar to that of conventional flocculants. This was because PAAD flocculants had a higher absorption capacity, and larger chain extending space than conventional linear flocculants, which could refrain from the entanglement of linear polymer chains and significantly improve flocculation capacity.