Here we report a facile method to fabricate composite polymeric/inorgainc shells consisting of poly(allylamine hydrochloride) (PAH)/poly-(sodium 4-styrenesulfonate) (PSS) multilayers strengthed by the in situ formed silica (SiO) nanoparticles (NPs), achieving an enhanced stability under harsh acidic and basic conditions. While the unsiliconised PAH/PSS multilayers show a pH-dependent stability and permeability, the composite PAH/PSS/SiO shells display significantly higher chemical tolerance towards a variety of harsh conditions (1 ≤ pH ≤ 13, high salinity). Upon treatment with either hydrochloric acid (HCl, pH=1) or 0.2 M ethylenediaminetetraacetic acid disodium salt (EDTA, weak acid, chelator), the (PAH/PSS)/SiO shells are able to maintain the integrity of most calcium carbonate (CaCO) particles, as the shells are tickened and densified by sufficient SiO NPs. When treated with NaOH solution at pH=13, the (PAH/PSS)/SiO shells also display an intact morphology and maintain the ability to intercept rhodamin B (Rh-B) molecules, which is quite different to that observed with the unsiliconised (PAH/PSS) shells. Ultrasound is proved to rapidly break the composite shells, hence can be used as a potential stimulus to trigger the release of encapsulated substances. All the results demonstrate the fact that the composite (PAH/PSS)/SiO shells have a higher chemical stability, lower permeability for small molecules and a greater sensitivity to ultrasound, which is promising for many applications where protecting the activity of small molecules is required, such as the delivery of encapsulated drugs in an unhindered form to their specific destination within the human body.