A method of forming a laminate and a method of manufacturing a photovoltaic device using the laminate are provided. The laminate forming method includes a first step of forming an intermediate layer on a base member, and a second step of forming a metal layer on the intermediate layer, the adhesion of the metal layer to the base member being lower than that of the intermediate layer, the reflectance of the metal layer being higher than that of the intermediate layer. The rate of formation of the metal layer is increased at an intermediate stage in the second step. The laminate thereby formed has improved characteristics and is capable of maintaining improved reflection characteristics and adhesion even under high-temperature and high-humidity conditions or during long-term use.