In China，the structure of poverty alleviation is transformed from Government-oriented to polycentric：the government，the market，the society and the impoverished groups. The charitable trust will motivate the charitable organization and the trust company to join the Participatory Poverty Alleviation Initiative through the innovative method-Social Finance. In order to promote the transformation of the network governance by the charitable trust，the key steps include to realize the charitable goal，to change the gap between rich and poor，and to build the all-round well-off society. Based on the theory of network governance，this article analyzes the relationships between the government，the market and the society after the implementation of the charitable trust innovation. In order to construct a model of network governance in poverty alleviation，two cases are introduced：The first is the Puhui Financial Charitable Trust in Shanxi Province to change the three interactions. The second contains eight new charitable trusts which are engaged in the poverty alleviation. Based on the case studies，the pattern of the participators and the resource integration process is concluded. The result will be the transformation from the participatory structure to the network structure，which takes advantage of charitable trust in the system and capacity modernization process of national governance in poverty alleviation.