Abstract: The amorphous alloys are a kind of interesting and promising material in material science. Owing to its special structural character and electronic properties, it provides a path to novel, more active and selective catalysts. Although experimental works on amorphous alloy could be found everywhere, a few theoretical calculations were published in literatures. It does give a challenge to theoretical researcher since it is not easy to model the amorphous structure. Until now, a controversy of the direction of charge-transfer still exists in the study of the Co-B amorphous alloy. According to the experimental results, the charge transfer between Co and B in Co-B amorphous alloy is from B to Co, which seems to be incompatible with the electronegative view in classical chemistry. On the other hand some theoretical calculations showed an opposite conclusion to the experiment. Since many physical and chemical properties like specific heat, magnetic susceptibility, ferromagnetism, superconductivity and catalytic activity are directly related to the electronic properties of the local structure of amorphous alloy, in this case, the charge transfer between Co and B are required to clarify the argument. The previous calculations were, unfortunately, not complete in many aspects; at the very least, the calculated models and methods were too rudimentary. The aim of our present paper is to investigate the electron transfer between B and Co of Co-B amorphous alloy by a series of cluster model ComB2(m=1~4) and Co-B calculations with density functional theory (DFT). Since most of the modeling and simulation concerning amorphous alloy were based on statistical method, which lays emphases on the long-range disordered, they give little information of electronic properties. In order to understand the electronic properties of amorphous alloy in detail, the best way is to calculate it by using a proper model with a correct local structure referring to the experimental fact at the precise level of quantum chemistry calculation. Hence, the present work tries to use a kind of new models. The models are constructed according to the following experimental results: amorphous alloy are packed by small clusters, its local structure is in ordering, and the metal-metalloid is chemically bonded. Our present paper, considering the direct B-B contact in cluster model is the key point that makes our calculations differ from the previous theoretical works. The results of the calculations showed that boron is an electron-donor, while cobalt is an electron-acceptor, which agrees well with the experimental results. It is very possible for Co-B amorphous alloy to exist the direct B-B contact. Compared with the calculation results from another series of ConB(n=1~4) cluster models, It could be concluded that the ComB2(m=1~4 ) clusters is more reasonable for the structure of Co-B amorphous alloy.