Hybrid films consisting of Sumecton SA smectite (SSA) and a diacetylenic two-photon absorptive dye; 1,4-bis(2,5-dimethoxy-4-{2-[4-(N-methyl)pyridinium]ethenyl}phenyl) butadiyne triflate (MPPBT) were fabricated. The MPPBT-clay composites were prepared by the cation exchange method in a dimethylsulfoxide (DMSO)-water mixed solvent. A low-light-scattering film, suitable for use in optical devices, was obtained by filtration of the dispersion of the MPPBT-clay composites. Estimation of the two-photon absorption cross-section (σ(2)) by means of the open-aperture Z-scan technique was performed using the present film. The σ(2) value of MPPBT in the film fabricated at the MPPBT loading levels vs. 20% cation exchange capacity was 1030 GM (1 GM= 1 × 1050 cm4 s photon−1 molecule−1) at an excitation wavelength of 800 nm. The value was 1.3 times greater than the maximum value of the σ(2) of MPPBT diss lved in DMSO with ut clay.