Lattice engineering of nanomaterials holds promise in simultaneously regulating their geometric and electronic effects to promote their performance. However, local microenvironment engineering of Fe 0 nanoparticles (nFe 0 ) for efficient and selective environmental remediation is still in its infancy and lacks deep understanding. Here, we present the design principles and characterization techniques of lattice-doped nFe 0 from the point of view of microenvironment chemistry at both atomic and elemental levels, revealing their crystalline structure, electronic effects, and physicochemical properties. We summarize the current knowledge about the impacts of doping nonmetal p-block elements, transitionmetal d-block elements, and hybrid elements into nFe 0 crystals on their local coordination environment, which largely determines their structure−property−activity relationships. The materials' reactivity−selectivity trade-off can be altered via facile and feasible approaches, e.g., controlling doping elements' amounts, types, and speciation. We also discuss the remaining challenges and future outlooks of using lattice-doped nFe 0 materials in real applications. This perspective provides an intuitive interpretation for the rational design of lattice-doped nFe 0 , which is conducive to real practice for efficient and selective environmental remediation.