Having won the fight against poverty in 2020, China entered the post-poverty era in its economic and social development. Vocational education embarks on a new anti-poverty journey. Cumulative advantages have been made for vocational education to fight poverty in the post-poverty era in the following aspects: the continuous efforts from the top-level design of the vocational education reform, the remarkable achievements of vocational education in poverty alleviation, and the steady advancement of the rural revitalization strategy. Developmental challenges are as follows: the poverty alleviation function of vocational education skills is weakened due to the in-depth changes in industrial technology, insufficient endogenous motivation from the anti-poverty targets in vocational education gives rise to the risk of returning to poverty, and the lack of precision in anti-poverty management leads to the reduction of anti-poverty effect in vocational education. Based on the new situation, new tasks and new demands of vocational education to fight poverty, it is necessary to reconstruct the human resources supply function for vocational education, reshape the ecological structure of anti-poverty consciousness in vocational education and improve the anti-poverty governance system in vocational education for sustainable development.