Ordered mesoporous boron-doped carbons (BOMCs) were prepared by co-impregnation and carbonization of sucrose and 4-hydroxyphenylboronic acid into SBA-15 silica template. Nitrogen sorption, small angle X-ray diffraction (XRD), and transmission electron microscopy (TEM) reveals that BOMCs possess highly ordered mesoporous structure, uniform pore size distribution, and high surface area. X-ray photoelectron spectroscopy (XPS) analysis demonstrates that B atoms can be successfully doped into the framework of OMCs. Due to the desirable characteristics of BOMCs, BOMCs are highly active, cheap, and selective metal-free electrocatalysts for the oxygen reduction reaction (ORR) in alkaline solution. Although B content is a key factor in determining ORR activity, the ORR activity of BOMCs is also dependent on the surface area. The high surface area of BOMCs facilitates the exposure of the active sites for ORR. BOMCs may be further exploited as potentially efficient and inexpensive metal-free ORR catalysts with good long-term stability in alkaline solution.