Novel and less toxic quantum dot (QD) semiconductors are desired for developing environmentally benign colloidal quantum dot solar cells. Here, the synthesis of novel lead/cadmium-free neodymium chalcogenide Nd-2(S, Se, Te)(3) QDs via solution-processed method is reported for the first time. The results show that small-bandgap semiconductor QDs with a narrow size distribution ranging from 2 to 8 nm can be produced, and the wide absorption band can be achieved by the redshift owing to the size quantization effect by controlling the initial loading of chalcogenide precursors. By analyzing the band structure of QDs and the energy level alignment between QDs and TiO2, the influence of energy offset between the conduction band edges of QDs and TiO2 on the charge transfer dynamics and photovoltaic performance of QD solar cells (QDSCs) is investigated. It is revealed that among the three types of QDs studied, Nd2Se3 QDSCs with the smallest energy offset exhibit the best performances and a decent power conversion efficiency of 3.19% is achieved. This work clearly demonstrates the promising potentials of novel rare earth chalcogenide quantum dots in photovoltaic applications.