To reveal the mechanisms of the influence of Ca2+ on membrane fouling with humic acid (HA), the adhesion forces of HA with both other HA molecules and the membrane, the HA fouling layer structure, HA fouling experiments, and the HA rejections at a wide range of Ca2+ dosages were investigated. The results indicated that the effect of Ca2+ on HA fouling can be divided into three stages. At lower ionic strength (IS) of CaCl2, the change in electrostatic forces is the main factor in controlling HA fouling behavior; i.e., increasing Ca2+ dosages resulted in more serious membrane fouling. When the IS of CaCl2 reached 10 mM, HA aggregates became the dominant factor in the fouling process, which could result in a porous fouling layer accompanied by less membrane fouling. Interestingly, much weaker membrane fouling was observed when the IS increased to 100 mM and the HA rejection began to decline. This was because a stronger hydration repulsion force was generated, which could weaken the compactness of the fouling layer and the adhesion forces of HA with both the membrane and HA, while enabling smaller-sized HA to pass more easily into the permeate, which led to less membrane fouling and a lower HA rejection.