Synthetic asymmetrical systems, Janus particles and patchy particles, are capable of undergoing hierarchical assembly processes that mimic those of Nature, to serve as switchable devices, optical probes, phase-transfer catalysts, and multifunctional drug carriers, each of which benefits from opposing surface patterns that behave differently. Production of nanometer-sized Janus particles that are equipped with efficient chemistries remains a challenge. A robust Janus-faced polymer nanoparticle framework that presents two orthogonally click-reactive surface chemistries has been generated by a recyclable strategy that involves reactive functional group transfer by templating against gold nanoparticle substrates. This anisotropic functionalization approach is compatible with a wide range of soft materials, providing Janus nanoparticles for the construction of dual-functionalized devices by accurately controlling chemical functionality at the nanoscopic level.