Flocculation has been a key issue for fiber cement manufacturing since cellulose or poly(vinyl alcohol) (PVA) fibers are used to replace asbestos. Due to the complexity of flocculation, many fiber cement companies face difficulties in optimizing it, which leads to unpredicted production problems and lower process efficiency. This paper studies the behavior of a dual system (PFR/PEO) and compares it with two anionic polyacrylamides commonly used in this industry. The work was carried out using a focused beam reflectance measurement as a sensor to monitor the flocculation process in real time. Results show that the proposed alternative dual system induces the formation of larger but less stable flocs than the ones obtained with the anionic polyacrylamides. A flocculation mechanism was proposed for the dual system consisting of the initial adsorption of the phenol-formaldehyde resin (PFR) onto the particles, which provides junction points for bridge formation by poly(ethylene oxide) (PEO). The flocculation kinetics induced by the dual system is determined by the PFR dosage.