I–III–VI2 group “green” quantum dots (QDs) are attracting increasing attention in photoelectronic conversion applications. Herein, on the basis of the “simultaneous nucleation and growth” approach, Cu–In–Ga–Se (CIGSe) QDs with light harvesting range of about 1000 nm were synthesized and used as sensitizer to construct quantum dot sensitized solar cells (QDSCs). Inductively coupled plasma atomic emission spectrometry (ICP-AES), wild-angle X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) analyses demonstrate that the Ga element was alloyed in the Cu–In–Se (CISe) host. Ultraviolet photoelectron spectroscopy (UPS) and femtosecond (fs) resolution transient absorption (TA) measurement results indicate that the alloying strategy could optimize the electronic structure in the obtained CIGSe QD material, thus matching well with TiO2 substrate and favoring the photogenerated electron extraction. Open circuit voltage decay (OCVD) and impedance spectroscopy (IS) tests indicate that the intrinsic re...