This study presents a simple and innovative approach for producing one-dimensional Mn5Si3 nanorods through a casting-extraction process. In this technique, the Mn5Si3 nanorods were synthesized by reacting Mn and Si during brass solidification and extracted by electrochemical etching of the brass matrix. The effect of the cooling rate during casting on the nanorods’ dimension, morphology, and magnetic properties was investigated. The results demonstrate that the prepared high-purity Mn5Si3 nanorods had a single-crystal D88 structure and exhibited ferromagnetism at room temperature. The morphology of the nanorods was an elongated hexagonal prism, and their preferred growth was along the [0001] crystal direction. Increasing the cooling rate from 5 K/s to 50 K/s lead to a decrease in the dimension of the nanorods but an increase in their ferromagnetism. At the optimal cooling rate of 50 K/s, the nanorods had a diameter and length range of approximately 560 nm and 2~11 μm, respectively, with a highest saturation magnetization of 7.5 emu/g, and a maximum coercivity of 120 Oe. These properties make the fabricated Mn5Si3 nanorods potentially useful for magnetic storage applications, and this study also provides a new perspective on the preparation of one-dimensional nanomaterials.