The study of non precious metal electrocatalysts with the purpose to replace expensive Pt catalyst has become a central theme in fuel cell communities. Certain types of N-containing transition metal catalysts have showed high activity for oxygen reduction in alkaline media, especially for Fe- and Co- centered catalysts [1-3]. However, compared to Pt-based catalysts for practical application in fuel cells, both the ORR activity and stability of these catalysts have to be significantly improved. Recently, template method has drawn great attention to obtain the specified morphology and predetermined microstructure [4,5]. In particular, the high surface area, high porosity and proper pore structure of catalyst usually lead to high catalytic activity for the ORR. However, there are some key factors that influence the systhesis of high-surface-area carbon materials, such as metal precusor, carbon precusor, template and so on. In this work, using poly(ethyleneimine) (PEI) as source of both N and C, and the nanoscale SiO₂ as basically sacrificial supports to create pores, the effects of metal valence states on the formation of N-doped carbon materials and its catalytic activity toward oxygen reduction reaction (ORR) are investigated by applying FeSO₄ and Fe₂(SO₄)₃ as the metal precursors in terms of the size of pore structure, the distribution of pore ratios and the graphitization of carbon.