Abstract: In this work, we investigated the energy transfer (EnT) and electron transfer (ET) processes as well as their relationship in the carbon quantum dots/rhodamine B (CQDs/RhB) including o-CQDs/RhB and m-CQDs/RhB systems by using photoluminescence spectroscopy in combination with steady-state and transient absorption spectroscopy. We found that the ET process is negligible in the o-CQDs/RhB system with an EnT efficiency as high as 73.2%, while it becomes pronounced in the m-CQDs/RhB system whose EnT efficiency is lower than 33.5%. Such an interplay of EnT and ET processes revealed in the prototypical composite system consisting of carbon quantum dots and dye molecules would provide helpful insights for applications of relevance to exciton quenching.