Surfactant free synthesis of metallic nanomaterials offers multiple benefits in medical, pharmaceutical, biological, biomedical, and catalytic application due to their high surface-to-volume ratio and fascinating physicochemical properties. Though there are several techniques with different advantageous and challenges in synthesis metal oxide or metallic nanomaterials have been investigated, the biocompatibility, stability, and purity of such nanomaterials also controllability with reproducibility are most challenging issue faced by researcher and scientist. Moreover, the metal oxide and metallic nanoparticles due to variation in size and shape and percentage of reduction are prone to lose reactivity and ultimately therapeutic efficacy, as this can precipitate out or form aggregate as bulk metals; therefore, various stabilizers briefly surfactant or allied materials are typically required. Plant-based is an alternative technique to synthesize stable metal oxide or metallic nanoparticles, however bench to market of such techniques is not yet well-setup, thus several surfactant-free strategies such as solvent mediated synthesis, ion-mediated synthesis, and several physical processes have been introduced for fabrication of oxide and reduced metallic nanoparticles as eco-friendly techniques by avoiding use of toxic chemicals. Thus, this chapter provides a brief on the utilization of surfactant free synthesis process for manufacturing of metallic nanomaterials with their associated applications and challenges.