Acids such as aqua regia, a 3:1 mixture of hydrochloric acid (HCl) and nitric acid, that contain strong oxidizing agents are used in the dissolution-based recovery of platinum group metals (PGMs). However, nitrate-nitrogen emission has become subject to increasingly strict environmental regulations in recent years. Accordingly, we herein propose a dissolution process for PGMs via the formation of complex oxides using HCl alone. We prepared complex oxides of alkali metals and rhodium (Rh), which is particularly hard to dissolve, and investigated their dissolution behaviors in HCl. Rh-containing complex oxides were prepared by calcining Rh powder and alkali metal salts in air, and dissolution tests using HCl were conducted on the complex oxides obtained. It was found that Rh-containing complex oxides were completely dissolved under appropriate calcination and dissolution conditions.