A robust method for the synthesis of new bio-based silane coupling agents (SCAs) by iridium-catalyzed hydrosilylation of naturally-occurring terpenoids and malonates modified with allyl groups is described. Iridium catalyst promotes regio- and chemoselective addition of triethoxysilane to allyl moieties in the presence of di- and trisubstituted C=C bonds, leading to the exclusive formation of β-silylated products. The application of easily accessible and cheap terpenoid substrates in place of fossil fuel sources complies with the Agenda 2030 for Sustainable Development, established by the United Nations. All synthesized bifunctional silanes were fully characterized by spectroscopic methods. Obtained products formed a new class of SCAs based on raw materials of natural origin. They showed potential as effective, biogenic SCAs for the preparation of silica-reinforced styrene-butadiene composites with improved essential parameters (rolling resistance, dry handling predictors, and elongation at break) for the production of “Green Tires” characterized by lower fuel consumption and increased driving safety.