Here, hierarchical nanostructures of clay-based hybrids were synthesized via a space-confined growth of layered basic zinc acetate (LBZA) nanosheets standing upright on both sides of bentonite clay platelets. These thermally instable LBZA nanosheets were thermally decomposed and fragmented into ZnO nanoparticles well-dispersed on bentonite platelets. The morphology and structure of LBZA/bentonite and ZnO/bentonite was characterized by SEM, TEM, XRD, TG-DSC, and FTIR. Surface density of LBZA nanosheets on bentonite platelets was simply controlled by tuning the amount of zinc acetate. LBZA/bentonite and ZnO/bentonite was used for the adsorption of Congo red (CR) and photodegradation of methyl orange (MO), respectively. Results showed that LBZA/bentonite exhibited higher adsorption capacity for Congo red (CR) than original bentonite. In addition, bentonite-supported ZnO nanoparticles efficiently promoted the photodegradation of MO under UV light irradiation.