The intercalation compounds (Polyaniline)(1.08)Mn0.86PS3 and (Polyaniline)(0.57)Cd0.73PS3 have been synthesized by the ion-exchange procedure. These compounds constitute a new family of intercalates in MPS3 (M = Mn, Cd) host layer, with Polyaniline as guest species. They have been characterized by powder X-ray diffraction (XRD), Fourier transform infrared (FTIR), differential thermal analysis (DTA), thermogravimetric analysis (TGA), and electrical conductivity measurements. Both intercalation compounds show values of electrical conductivity (sigma(i)) of about 10(-7) Ohm(-1) cm(-1) at 298 K and photoconductivity at temperatures from 296 to 343 K.