Nanoflower-like MoS₂ deposited on the surface of rectangular CaTiO₃(CTO) was designed and synthesized via a simple template-free strategy. Through SEM, TEM, and other characterization methods, the MoS₂ nanoflowers were confirmed to be well deposited on the surface of CTO. LED was used as the visible light source, and rhodamine B (RhB) in an aqueous solution was used as the model pollutant to assess the photodegradation activity of the samples. The results showed that the MoS₂/CaTiO₃(MCTO) composite significantly improved the photocatalytic degradation of rhodamine B (RhB) in water, compared with a single CTO, and with the MCTO-2 composite photocatalysts, 97% degradation of RhB was achieved in 180 min, and its photocatalytic activity was about 5.17 times higher than that of the bare CTO. The main reasons for enhancing photocatalytic performance are the strong interaction between the nanoflower-like MoS₂ and rectangular CTO, which can lead to the effective separation of electron transfer and photoexcited electron–hole pairs in MCTO composites. This work provides a new notion for researching an effective method of recycling catalytic materials.