Calcined and organo-modified Zn-Al layered double hydroxides (LDHs) were studied as adsorbents and photocatalysts for removal of cationic dye, as namely methylene blue (MB). Zn-Al LDHs with a cationic ratio of 2:4 were obtained by the coprecipitation method. As-synthesized samples were calcined at different temperatures and the phase transformations were investigated by XRD, TG/DTG, and UV-vis-DR methods. The activity of as-synthesized and calcined Zn-Al LDHs under UV light was attributed to the presence of ZnO phase. The amount of ZnO in LDHs can be regulated by varying of Zn/Al ratio and heating temperature. The impact of Zn/Al ratio on photocatalytic activity of LDHs was observed predominant. The calcined Zn-Al LDHs demonstrated low adsorption of MB. The modification of ZnAl LDHs by sodium dodecyl sulfate was performed using a reconstruction method. The organo/LDH nanohybrids demonstrated high adsorption capacity to MB. The removal of MB from solutions with organo/Zn-Al LDHs was enhanced by using UV light due to MB photodestruction.