In this study, silver/polyimide (Ag/PI) composite films with enhanced heat dissipation properties were prepared. Ag was formed by reducing AgNO at various locations according to the reduction method. Two different types of soluble PIs capable of solution processing were used, namely Matrimid and hydroxy polyimide (HPI). Unlike Matrimid with bulky substituents, HPI with polar hydroxy groups formed ion-dipole interactions with Ag ions to form Ag particles with uniform size distribution. The location and distribution of Ag particles affect the heat emission characteristics of the composite films, resulting in better heat dissipation properties with the thermally and photochemically reduced Ag/HPI films having more Ag particles distributed inside of the films than the chemically reduced films.