To elucidate the structure-performance relationship of the new potential cathode materials AFe(SO4)2 ([Formula: see text], Na, K) compared with LiFePO4, first-principles calculations are performed to investigate the structure, mechanical stabilities and electronic properties of them. The calculated results show that AFe(SO[Formula: see text] ([Formula: see text], Na, K) compounds are mechanically stable and exhibit strong anisotropy. LiFe(SO[Formula: see text], NaFe(SO[Formula: see text] and KFe(SO[Formula: see text] are more brittle and have higher elastic modulus than LiFePO4, which is attributed to the strong chemical bonding of them. Electronic structure are predicted by HSE06 functional and the band gaps are 5.006, 4.996, 5.146 and 3.711[Formula: see text]eV for LiFe(SO[Formula: see text], NaFe(SO[Formula: see text], KFe(SO[Formula: see text] and LiFePO4, respectively. Full ab initio molecular dynamics simulations are performed to calculate the mean square displacements and diffusion coefficients of the alkali-ion. NaFe(SO[Formula: see text] has large diffusion coefficient as [Formula: see text][Formula: see text]m2/s at 1273[Formula: see text]K, as well as larger activation energy as 0.167[Formula: see text]eV. All the results contribute to understand the microscopic origin of the different behaviors of intercalation cathode used in rechargeable battery.