Within the pulp and paper industry, the recycling of whitewater to reduce fresh water consumption and effluent volume leads to an accumulation of dissolved and colloidal substances (DCS) in the papermaking wet-end system. DCS interacts with certain electrolytes and polyelectrolytes to form non-ionic DCS interferents (pitch deposits and depositions), which adversely affect papermaking. Polyethyleneimine (PEI), a fixing agent with a low molecular weight and high cationic charge density, can control the DCS in the wet-end system. The fixation efficiency of DCS simulacra and the wet-end properties were explored under varying Ca2+ and PEI concentrations in pulp. The fixation and retention efficiency of DCS simulacra were improved, the zeta potential of pulp and drainage rate of pulp increased, and the cationic demand of pulp filtrate decreased with increasing PEI dosage. Ca2+ shielded the negatively charged ions on the surface of the fibers and DCS simulacra, influenced the fixation efficiency of PEI to DCS simulacra, and improved the drainage rate of pulp.