In this paper, a method is presented for the preparation of a transparent thin solid film by stacking alpha-zirconium phosphate nanosheets (alpha ZrPNSs), and intercalating with cationic free-base porphyrin (TMPyP) molecules at the interlayer space. The alpha ZrPNSs staked solid films with high transparency were firstly prepared by the filtration-film transfer method of a alpha ZrPNSs colloid suspension. Immersion of the transparent film into a mixed aqueous solution of the TMPyP and n-butylamine was found to be the most effective intercalation method. In this film, the TMPyP cations existed as monomer species.