A carbon–carbon-linked, ultrathin, two-dimensional (2D) polymer film was prepared at the air/water interface through photochemically triggered [2 + 2] cycloaddition. The preorganization of the monomers on the water surface and the subsequent photo-polymerization led to the successful preparation of the ultrathin 2D polymer film. The obtained film is continuous, free standing, and has a large area (over 50 μm2). Transmission electron microscopy (TEM) and atomic force microscopy (AFM) give clear evidence of the ultrathin film morphology. Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) indicate successful photo-induced [2 + 2] polymerization.