Market-based initiatives like agriculture value chain (AVC) are becoming progressively pervasive to support smallholder rural farmers and assist them in entering larger market interventions and providing a pathway of enhancing their socioeconomic well-being. Moreover, it may also foster staggering effects towards the post-era poverty alleviation in rural areas and possessed a significant theoretical and practical influence for modern agricultural development. The prime objective of the study is to explore the effects of smallholder farmers’ participation in the agricultural value chain for availing rural development and poverty alleviation. Specifically, we have crafted the assessment employing pre-production (improved fertilizers usage), in-production (modern preservation technology), and post-production (supply chain) participation and interventions of smallholder farmers. The empirical data has been collected from a micro survey dataset of 623 kiwifruit farmers from July to September in Shaanxi, China. We have employed propensity score matching (PSM), probit, and OLS models to explore the multidimensional poverty reduction impact and heterogeneity of farmers’ participation in the agricultural value chain. The results show that the total number of poor farmers who have experienced one-dimensional and two-dimensional poverty is relatively high (66.3%). We also find that farmers’ participation in agricultural value chain activities has a significant poverty reduction effect. The multidimensional poverty level of farmers using improved fertilizer, organizational acquisition, and using storage technology (compared with non-participating farmers) decreased by 30.1%, 46.5%, and 25.0%, respectively. The multidimensional poverty reduction degree of male farmers using improved fertilizer and participating in the organizational acquisition is greater than that of women. The multidimensional poverty reduction degree of female farmers using storage and fresh-keeping technology has a greater impact than the males using storage and improved storage technology. Government should widely promote the value chain in the form of pre-harvest, production, and post-harvest technology. The public–private partnership should also be strengthened for availing innovative technologies and infrastructure development.