<p>Spinel-type Li₄Ti₅O₁₂ (LTO) has attracted considerable attention as an anode material for lithium-ion batteries due to its excellent cycle stability, high safety, and zero-strain insertion characteristics. However, its practical application is limited by intrinsically low electronic conductivity and moderate lithium-ion diffusion kinetics. Doping with aliovalent elements, such as Al³⁺, has emerged as an effective strategy to overcome these limitations by enhancing both electronic and ionic transport properties. While various synthesis methods, such as solid-state reactions and sol–gel processes, have been explored for preparing doped LTO, flame spray pyrolysis (FSP) has been considered as a promising technique due to its rapid processing and ability to produce particles with controlled composition and morphology. In this study, Al-doped LTO was synthesized for the first time using the FSP method. Although Al doping is known to enhance electronic properties, its effect on LTO synthesized via FSP has not been previously investigated. Remarkably, the incorporation of Al resulted in significant suppression of particle and crystallite growth. Furthermore, solid-state ²⁷Al MAS NMR confirmed uniform Al distribution across both 8a and 16d sites in a near-theoretical ratio, a feature rarely achieved with conventional synthesis methods. In addition, electrochemical impedance spectroscopy revealed enhanced electrical conductivity with increasing Al content, attributed to improved charge compensation via partial reduction of Ti⁴⁺ to Ti³⁺. These findings highlight the unique capability of FSP to produce high-performance Al-doped LTO with controlled structure and composition, offering a superior alternative to traditional solid-state routes.</p> Graphical Abstract <p></p>