Nanocomposite based on polyaniline (PANI) and α-zirconium phosphate (α-ZrP) has been synthesized by in situ polymerization using aniline intercalation compound (ANI)/ZrP as intermediate. Aniline was successfully intercalated into the interlayer spacing of crystalline α-ZrP forming a double-phase intermediate by adsorption. The intercalated aniline was polymerized by adding appropriate amount of ammonium peroxodisulphate (APS) solution. The synthesized nanocomposites were characterized by XRD, SEM, and FT-IR. X-ray diffraction patterns showed that PANI was formed outside α-ZrP. TGA/DSC analysis showed improved thermal stability for the PANI/ZrP nanocomposite in comparison with pure PANI. The PANI/ZrP nanocomposite was studied by cyclic voltammetry (CV), which revealed good redox activity and electrochemical-cycling stability in acidic solution. The interaction between PANI and nanosheets greatly affected the electrochemical behavior of PANI/ZrP nanocomposite. The electrochemical behavior of PANI/ZrP nanocomposite in HCl solution with different pH values has been studied in detail.