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 15–20nm and 5nm, 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. The LMS/CNFs exhibit an excellent cycling stability with a capacity retention of 96% for up to 150 cycles at voltages of 1.5–4.75V vs. Li/Li+ and a current rate of 33.3mAg−1. The cycling stability of the LMS/CNFs results from the nano-architecture formed between the LMS NRs and the CNFs.