Resettlement will change the stock and structure of livelihood capital of ecological emigrant families and make their livelihood pattern change. Taking ten resettlement sites for implementing poverty alleviation in Guizhou Province as samples, this paper conducts a survey of livelihood capital to obtain the relevant data on the livelihood of migrants, and then conducts a comprehensive evaluation on the livelihood capital of immigrants and analyzes the interaction between the family livelihood capital and livelihood models. The empirical analysis shows that both the total amount and the structure of the livelihood capital of the emigrated families have changed significantly before and after the relocation, that the natural capital is reduced after relocation, material capital and social capital are little rising but financial capital increases mostly. Agricultural production business income declines, but other incomes are obviously rising. When the emigrants stay in new families, the improvement of their livelihood capital operation efficiency is not significant, however, after two years, the improvement is significantly rising. The emigrant family income structure change has negative effect on their livelihood capital operation efficiency, their livelihood model selection is possibly not proper. Thus, the livelihood development of ecological emigrant family has an adaptive process and the government should actively help the emigrants realize the matching and interactive improvement between ecological model and livelihood capital at new living places as soon as possible to boost the sustainable development of ecological emigrant families.