Adsorption and intercalation of +1 charged cationic dihydroxo(tetraphenylporphyrinato)antimony(V) bromide (1a) into an artificially synthesized smectite clay was studied. The red shift of Soret band of 1a was observed in an aqueous clay suspension owing to the adsorption onto the clay. Analyses of X-ray diffraction of the obtained complex between 1a and the clay indicate the intercalation of 1a into the clay interlayer. Hydroxo group as an axial ligand led to the effective intercalation of la into the clay.