Rhenium disulfide (ReS2) is an interesting kind of transition metal dichalcogenide (TMD) because of its thickness-independent and suitable direct-bandgap structure, which could enable highly efficient solar-energy conversion efficiency. Here, we demonstrate an ultrasonic liquid exfoliation technique in combination with grinding to produce high quality ReS2 nanosheets (NSs) on a large scale. After combination with TiO2 nanoparticles, the co-catalytic performance of TiO2@ReS2 nanocomposites is investigated, which presents dramatically enhanced degradation activity of organic pigments under sunlight illumination in comparison with pure TiO2 nanoparticles. The underlying mechanism of enhanced photocatalytic activity can be attributed to improved separation efficiency of photogenerated electron-hole pairs in TiO2@ReS2 nanocomposites, which is confirmed by photoluminescence analysis and photoelectrochemical measurements. Our results demonstrate that the layered ReS2 NS is a promising two-dimensional supporting platform for photocatalysis and moreover it could also provide a new perspective on TMDs co-catalyst.