We report on the improved electrochemical performance of a high-voltage LiNi0.5Mn1.5O4 (LNMO) cathode using surface-modified carbon blacks (CBs) as conductive agents. Facile modifications of CBs were achieved using thermal, urea-based hydrothermal, and acid oxidation treatments. The material properties of the modified CBs, LNMO-based electrode surface, and electrolyte compositions were investigated and correlated. Based on the distribution of the decomposition deposits on the surface of the electrode, it is confirmed that CB, rather than the LNMO active material, dominates the electrolyte decomposition site at a high voltage, owing to its relatively high surface area for the reaction. Additionally, compared with the pristine CB, the hydrothermally treated N-doped CB (HCB) improves the electrochemical performance of the LNMO cathode, although the thermally treated sample exhibits the most adverse influence, followed by the oxidized one. The LNMO/HCB cathode attains optimum capacity retention (approximately 95%) for 100 cycles (1 C) and a high rate capability (70%, 5 C/0.2 C), corresponding to a lowered resistance at the cathode–electrolyte interface. Furthermore, HCB with a limited specific surface area and increased defects, as well as additional pyrrolic-N and pyridinic-N groups, substantially reduces the decomposition deposits on the surface of the electrode and the decomposition products in the electrolyte. These phenomena account for the improved electrochemical performance of the LNMO/HCB cathode.