Sodium-ion batteries (SIBs) can develop cost-effective and safe energy storage technology for substantial energy storage demands. In this work, we have developed manganese oxide (α-MnO2) nanorods for SIB applications. The crystal structure, which is crucial for high-performance energy storage, is examined systematically for the metal oxide cathode. The intercalation of sodium into the α-MnO2 matrix was studied using the theoretical density functional theory (DFT) studies. The DFT studies predict Na ions' facile diffusion kinetics through the MnO2 lattice with an attractively low diffusion barrier (0.21 eV). When employed as a cathode material for SIBs, MnO2 showed a moderate capacity (109 mAh·g-1 at C/20 current rate) and superior life cyclability (58.6% after 800 cycles) in NaPF6/EC+DMC (5% FEC) electrolyte. It shows a much higher capacity of 181 mAh·g-1 (C/20 current rate) in NaClO4/PC (5% FEC) electrolyte, though it suffers fast capacity fading (11.5% after 800 cycles). Our findings show that high crystallinity and hierarchical nanorod morphology of the MnO2 are responsible for better cycling performance in conjunction with fast and sustained charge-discharge behaviors.