Minute Li2MnSiO4 nanorods embedded in carbon nanofibers (LMS/CNFs) are prepared via an ethanol-based solvothermal process, and then by electrospinning and subsequent carbonization processes. The LMS nanorods (NRs) have lengths and widths of 15–20 nm and 5 nm, respectively, and grow lengthwise, i.e., along the [010] direction, which facilitates Li-ion transport in the LMS during charging/discharging. In addition, these LMS NRs are well incorporated in the electrospun LMS/CNFs after carbonization.