Tunable core-shell Ag@Mesoporous SiO₂ spheres were synthesized via an in situ modified Stöber approach by varying the amount of ethanol (EtOH) expanding their potentials in many applications. Mesoporous silica was generated by adding tetraethyl orthosilicate (TEOS) to the mixture of colloidal Ag particles prepared by reducing silver nitrate (AgNO₃) with L-ascorbic acid and using hexadecyltrimethylammonium bromide (CTAB) as a template at the presence of ethanol and sodium hydroxide (NaOH) at pH 10 as a catalyst. The average sizes of the Ag cores at the three increasing volumes of ethanol were ~47 ± 6, 36 ± 4, and 11 ± 5 nm, while the silica particle size and the thickness of the silica shells increased, resulting in a blueshift of localized surface plasmon resonances (LSPR) of the Ag NPs. The corresponding specific surface areas of silica particles were 356 ± 10, 419 ± 20 and 490 ± 25 m² g⁻¹, and average pore diameters varied from 5.7, 5.0 to 3.3 nm according to BET and BJH analyses. TEM studies confirmed the core-shell structure, pore sizes and shapes of mesoporous shells. The dissolution tests demonstrated that the release of Ag from the powder samples is pH-sensitive and time-dependent.