Hollow carbon nanostructures have inspired numerous interests in areas such as energy conversion/storage, biomedicine, catalysis, and adsorption. Unfortunately, their synthesis mainly relies on template-based routes, which include tedious operating procedures and showed inadequate capability to build complex architectures. Here, by looking into the inner structure of single polymeric nanospheres, we identified the complicated compositional chemistry underneath their uniform shape, and confirmed that nanoparticles themselves stand for an effective and versatile synthetic platform for functional hollow carbon architectures. Using the formation of 3-aminophenol/formaldehyde resin as an example, we were able to tune its growth kinetics by controlling the molecular/environmental variables, forming resin nanospheres with designated styles of inner constitutional inhomogeneity. We confirmed that this intraparticle difference could be well exploited to create a large variety of hollow carbon architectures with desirable structural characters for their applications; for example, high-capacity anode for potassium-ion battery has been demonstrated with the multishelled hollow carbon nanospheres.