Metallized polymer films, used in many optical applications because of their high reflectivity, are usually prepared under complex conditions. In this work, a two-step autocatalytic deposition method was adopted to prepare an Agdeposited polyvinyl chloride (PVC) film (Ag/PVC composite film) with high reflectivity. When Ag particles were used as a coating, the formed facecentered cubic crystal endowed a higher reflectivity than other crystals. Therefore, Pd metal was introduced as the catalytic center for Ag deposition to promote the formation of face-centered cubic crystals, thereby obtaining a highly reflective PVC film. Moreover, we improved the reflectivity of the Ag/PVC composite film by adjusting different process parameters, and the maximum reflectivity of the Ag/PVC composite film could reach as high as 93%. The twostep autocatalytic deposition we used was a simple, efficient, and low-energy method to prepare highly reflective films. The optimum process parameter was also significant for further research on highly reflective films.