Strong optical absorption by a semiconductor is a highly desirable property for many optoelectronic and photovoltaic applications. The optimal thickness of a semiconductor absorber is primarily determined by its absorption coefficient. To date, this parameter has been considered as a fundamental material property, and efforts to realize thinner photovoltaics have relied on light-trapping structures that add complexity and cost. Here we demonstrate that engineering cation disorder in a ternary chalcogenide semiconductor leads to considerable absorption increase due to enhancement of the optical transition matrix elements. We show that cation-disorder-engineered AgBiS2 colloidal nanocrystals offer an absorption coefficient that is higher than other photovoltaic materials, enabling highly efficient extremely thin absorber photovoltaic devices. We report solution-processed, environmentally friendly, 30-nm-thick solar cells with short-circuit current density of 27 mA cm−2, a power conversion efficiency of 9.17% (8.85% certified) and high stability under ambient conditions.