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Red slipped and painted wares (RSW and RPW) were manufactured to cook, serve, or store foods and liquids in the middle Yangtze River valley (MYRV) of China some 8500 and 7800 years ago, respectively. Their primary use narrowed down to serving and drinking in the Upper Qujialing (5300–4500 cal BP) and Shijiahe (4500–4200 cal BP) periods when initial states (bang guo) took shape and developed in the region. The increasing social complexity in MYRV correlated with the formation of community and neighborhood identity through rituals and socio-economic ties involving the widespread use of RSW and RPW. How the two wares were produced and used helps us understand the relationships among productive activities, identity, and social inequality in MYRV. This paper presents the first overview of RSW and RPW in the Neolithic MRYV. It introduces a multi-analytical study of the two wares—mostly dating to the Shijiahe period—unearthed from the site of Fenghuangzui in Xianyang City of Hubei Province, China. Optical microscopic examination revealed that the paint of RPW—50 μm thick on average—was applied using a brush while the slip of RSW is thinner and finer and possibly formed by self-slipping. Handheld X-ray fluorescence (hhXRF) and benchtop micro-XRF analyses ascribed the red paint or slip to iron and iron oxide. Raman and X-ray absorption fine structure analyses confirmed that iron was present in the paint or slip in the form of hematite with a poorly developed crystalline structure. Furthermore, thin-section petrography implied that different pastes were used to produce RPW and RSW, and hhXRF data indicated that the Upper Qujialing and Shijiahe pottery differ in the concentrations of five elements (Zr, Fe, Mn, Ti, and Ba), which might be helpful in future provenance studies of RSW and RPW. Our study discloses the complexity of the manufacture of RSW and RPW at Fenghuangzui. More details of RSW and RPW production and use from our ongoing project shall reveal the role of the two wares in the social dynamics of the Late Neolithic MYRV. [ABSTRACT FROM AUTHOR]