A gradient Si-rich oxide multilayer (GSRO-ML) deposition structure is proposed to achieve super-high density Si quantum dot (QD) thin film formation while preserving QD size controllability for better photovoltaic properties. Our results indicate that the Si QD thin film using a GSRO-ML structure can efficiently increase the QD density and control the QD size. Its optical properties clearly promise the capability of effective bandgap engineering even though these QDs are closely formed. The Si QD thin film using a GSRO-ML structure obviously reveals better electro-optical properties than those using a [silicon dioxide/silicon-rich oxide] multilayer ([SiO2/SRO]-ML) structure owing to the better optical absorption and carrier transport properties. Therefore, we successfully demonstrate that our proposed GSRO-ML structure has great potential for application in solar cells integrating Si QD thin films.