The polysilicate aluminum ferric (PSAF) was synthesized via copolymerization of polysilicic acid (PSi), AlCl3 and FeCl3 for treating oily wastewater from Daqing gas field. This study investigated the effects of key preparation factors such as the degree of PSi's preactivation and the ratio of (Fe + Al)/Si and Al/Fe on both polymerization and coagulation performance exhibited by PSAF. To determine the optimal timing for introducing Al3+ and Fe3+, zeta potential, viscosity and particle size were investigated. Additionally, infrared spectroscopy, X-ray powder diffraction, polarizing microscopy and scanning electron microscope analysis were employed to investigate the structure and morphology of PSAF. The results indicate that under conditions characterized by a SiO2 mass fraction of 2.5% and pH = 4.5, an optimal timing for introducing Al3+ and Fe3+ is at 100 min when PSi exhibits moderate polymerization along with sufficient stability. When considering molar ratios such as (Al + Fe)/Si being 6:4 and Al/Fe being 5:5, respectively, PSAF falls within a “stable zone” enabling storage period up to 32 days. Moreover, Jar test results demonstrate that at a dosage of 200 mg/L PSAF for oily wastewater treatment in gas fields could reach the maximum turbidity removal efficiency up to 99.5% while oil removal efficiency reach 88.6% without pH adjustment. The copolymerization facilitates the formation of larger PSAF aggregates with positive potential, thereby augmenting the coagulants' adsorption bridging and charge neutralization capabilities. As a result, PSAF has great potential as a practical coagulant for treating oil-containing wastewater in industrial settings.