Herein we highlight the significance of nanoscale attachment modality as an important determinant of observed electrochemical performance. Specifically, controlled loading ratios of multi-walled carbon nanotubes (MWNTs) have been successfully anchored onto the surfaces of a unique "flower-like" Li4Ti5O12 (LTO) micro-scale sphere motif, for the first time, using a number of different and distinctive preparative approaches, including (i) a sonication method, (ii) an in situ direct-deposition approach, (iii) a covalent attachment protocol, as well as (iv) a pi-pi interaction strategy. In terms of structural characterization, the composites generated by physical sonication as well as non-covalent pi-pi interactions retained the intrinsic hierarchical "flower-like" morphology and exhibited a similar crystallinity profile as compared with that of pure LTO. By comparison, the composite prepared by an in situ direct deposition approach yielded not only a fragmented LTO structure, likely due to the possible interfering presence of the MWNTs themselves during the relevant hydrothermal reaction, but also a larger crystallite size, owing to the higher annealing temperature associated with its preparation. Finally, the composite created via covalent attachment was covered with an amorphous insulating linker, which probably led to a decreased contact area between the LTO and the MWNTs and hence, a lower crystallinity in the resulting composite. Electrode tests suggested that the composite generated by pi-pi interactions out-performed the other three analogous heterostructures, due to a smaller charge transfer resistance as well as a faster Li-ion diffusion. In particular, the LTO-MWNT composite, produced by pi-pi interactions, exhibited a reproducibly high rate capability as well as a reliably solid cycling stability, delivering 132 mA h g(-1) at 50 C, after 100 discharge/charge cycles, including 40 cycles at a high (> 20 C) rate. Such data denote the highest electrochemical performance measured to date as compared with any LTO-carbon nanotube-based composite materials previously reported, under high discharge rate conditions, and tangibly underscore the correlation between preparative methodology and the resulting performance metrics. (C) 2017 The Electrochemical Society. All rights reserved.