Abstract: In order to study the electron property and the microlocal structure of Co-P amorphous alloy，a series of single-P（ConP）and two-P（ConP2）cluster models were chosen according to the experiment fact of the possible presence of direct P-P contact and short-range-ordering in the amorphous alloy. ConP and ConP2 cluster models were calculated with the DFT method and calculations showed that P（phosphor）accepted electron from Co（cobalt）in single-P（Co2P（2），Co3P（1）and Co4P（2））cluster models，which agrees well with the Pauli electronegative rule，and a very strong interaction between Co and P resulted in formation stable clusters Co2P（2），Co3P（1）and Co4P（2）. However，two-P（ConP2）cluster models and single-P cluster Co5P（1）were unstable，and it was impossible to present direct P-P contact in two-P（ConP2）cluster models. It could be concluded that the clusters Co2P（2），Co3P（1）and Co4P（2） is more reasonable to represent the local structure of Co-P amorphous alloy.