Similar to translated thermal ablative techniques in clinic, the occurrence of cellular necrosis during tumor photothermal therapy (PTT) would induce inflammatory responses that are detrimental to therapeutic outcomes. Inspired by the well-known colorimetric Folin–Ciocalteu assay, monodispersed and renal-clearable tungsten (W)-based polyoxometalate nanoclusters (W-POM NCs, average diameter of around 2.0 nm) were successfully obtained here through a facile redox reaction with natural gallic acid in alkaline aqueous solution. Apart from excellent stability in the form of freeze-dried powder, the as-prepared W-POM NCs occupied considerable biocompatibility toward normal cells/tissues both in vitro and in vivo, since no obvious toxicities were observed by treating female Balb/c mice with concentrated W-POM NCs during the 30 day post-treatment period. More importantly, W-POM NCs exhibited not only considerable near-infrared (NIR) light absorption (coloration effect originated from the existence of electron-trapped W5+) for efficient PTT but also impressive anti-inflammatory ability (eliminating inflammation-related reactive oxygen species by the oxidation of W5+ into W6+ state) to achieve better therapeutic outcomes. Thus, our study pioneers the application of POMs for non-inflammatory PTT with expected safety and efficiency.