Rational nanoscale surface engineering of electroactive nanoarchitecture is highly desirable, since it can both secure high surface-controlled energy storage and sustain the structural integrity for long-time and high-rate cycling. Herein, ultrasmall MoS2 quantum dots (QDs) are exploited as surface sensitizers to boost the electrochemical properties of Li4Ti5O12 (LTO). The LTO/MoS2 composite is prepared by anchoring 2D LTO nanosheets with ultrasmall MoS2 QDs using a simple and effective assembly technique. Impressively, such 0D/2D heterostructure composites possess enhanced surface-controlled Li/Na storage behavior. This unprecedented Li/Na storage process provides a LTO/MoS2 composite with outstanding Li/Na storage properties, such as high capacity and high-rate capability as well as long-term cycling stability. As anodes in Li-ion batteries, the materials have a stable specific capacity of 170 mAhg(-1) after 20 cycles and are able to retain 94.1% of this capacity after 1000 cycles, i.e., 160 mAhg(-1), at a high rate of 10 C. Due to these impressice performance, the presented 0D/2D heterostructure has great potential in high-performance LIBs and sodium-ion batteries.