The invention belongs to the field of polymer/phyllosilicates composite material preparation and discloses a preparation process of poly-fluorine-containing acrylic ester/montmorillonite composite emulsion. The process is characterized by comprising the following steps: 1) adding sodium base montmorillonite clay in water to obtain a montmorillonite suspension, in the presence of the assistant intercalator, adding the montmorillonite suspension into an aqueous solution of cetyl trimethylammonium bromide to obtain organo-montmorillonite; 2) mixing the organo-montmorillonite, monomer I and monomer II to form a stable dispersion, adding the dispersion into the aqueous solution of complex emulsifying agent to form a stable pre-emulsion; and 3) adding the pre-emulsion into an agitated reactor, adding an initiator for the first time, heating to 70-75 DEG C, adding the initiator for the second time after the system emits blue light, carrying out isothermal reaction for 1-3h, heating to 80-85 DEG C and carrying out constant temperature reaction for 1-2h to obtain the poly-fluorine-containing acrylic ester/ montmorillonite composite emulsion. The preparation process has low cost, and obviously improved tensile strength, elongation at break and water tolerance of the prepared adhesive film.