Kesterite-based photovoltaic devices formed on flexible ceramic substrates are provided. In one aspect, a method of forming a photovoltaic device includes the steps of: forming a back contact on a flexible ceramic substrate; forming a kesterite absorber layer on a side of the back contact opposite the flexible ceramic substrate; annealing the kesterite absorber layer; forming a buffer layer on a side of the kesterite absorber layer opposite the back contact; and forming a transparent front contact on a side of the buffer layer opposite the kesterite absorber layer. A roll-to-roll-based method of forming a photovoltaic device and a photovoltaic device are also provided.