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This contribution reports on the synthesis and the main physical properties of n-type SnO₂ nanoparticles synthesized for the first time by a completely green chemistry process using Aspalathus linearis’s natural extract as an effective chelating agent. Their surface/interface and volume properties by X-rays diffraction, Raman, X-rays photoemission & photoluminescence spectroscopies are reported. Their average diameter ranging from 2.1 to 19.3 nm follows a thermal governed equation of <Ø_particles> = 1.048 10⁻⁵ T² – 4.92 10⁻³ T + 2.84. The smallest SnO₂ nanoparticles exhibit effective photocatalytic responses to Methylene blue, Congo red and Eosin Y.