To realize efficient and sustainable poverty alleviation, this study firstly investigated the identification of multidimensional poverty and relative poverty, and then explored relevant poverty alleviation pathways. Poverty levels in 31 provinces including the autonomous regions and municipalities of China were identified at the county level using the average nighttime light index (ANLI), county multidimensional development index (CMDI), and a method combining multidimensional poverty index and relative poverty standards. Poverty alleviation pathways for poverty-stricken counties were explored from the aspects of industry, education, tourism and agriculture. The results revealed that nearly 60% of counties in China were primarily under relative poverty, most of which were corresponded to light relative poverty. In terms of ANLI and CMDI, 63% and 79% of the national poverty-stricken counties, as of 2018, could be identified, suggesting that CMDI had a higher performance for identifying poverty at the county level. In terms of poverty alleviation pathways, 414, 172, 442, and 298 poverty-stricken counties were receptive to industry poverty alleviation, education poverty alleviation, tourism poverty alleviation, and agriculture poverty alleviation, and 61% of counties had more poverty-causing factors, implying that multidimensional poverty alleviation is suitable in most of the counties.