Abstract The adjustment of pH is an important way to enhance removal efficiency in coagulation units, and in this process, the floc size, strength and structure can be changed, influencing the subsequent solid/liquid separation effect. In this study, an inorganic polymer coagulant, polyferric chloride (PFC) was used in a low dissolved organic carbon (DOC) and high alkalinity surface water treatment. The influence of coagulation pH on removal efficiency, floc growth, strength, re-growth capability and fractal dimension was examined. The optimum dosage was predetermined as 0.150 mmol/L, and excellent particle and organic matter removal appeared in the pH range of 5.50–5.75. The structure characteristics of flocs formed under four pH conditions were investigated through the analysis of floc size, effect of shear and particle scattering properties by a laser scattering instrument. The results indicated that flocs formed at neutral pH condition gave the largest floc size and the highest growth rate. During the coagulation period, the fractal dimension of floc aggregates increased in the first minutes and then decreased and larger flocs generally had smaller fractal dimensions. The floc strength, which was assessed by the relationship of floc diameter and velocity gradient, decreased with the increase of coagulation pH. Flocs formed at pH 4.00 had better recovery capability when exposed to lower shear forces, while flocs formed at neutral and alkaline conditions had better performance under higher shear forces.