The widespread phase-out of long-chain per- and poly-fluoroalkyl substances (PFASs) has created an urgent need for durable, fluorine-free water-repellent finishes that match the performance of legacy chemistries while minimising environmental impact. Here, the performance of an eco-friendly hybrid organic–inorganic treatment obtained by the in situ hydrolysis–condensation of triethoxy(octyl)silane (OS) in an amino-terminated polydimethylsiloxane (APT-PDMS) aqueous dispersion was investigated. The sol was applied to plain-weave cotton and polyester by a pad-dry-cure process and benchmarked against a commercial fluorinated finish. Morphology and chemistry were characterised by SEM–EDS, ATR-FTIR, and Raman spectroscopy; wettability was assessed by static contact angle, ISO 4920 spray ratings, and AATCC 193 water/alcohol repellence; and durability, handle, and breathability were evaluated through repeated laundering, bending stiffness, and water-vapour transmission rate measurements. The silica/PDMS coating formed a uniform, strongly adherent nanostructured layer conferring static contact angles of 130° on cotton and 145° on polyester. After five ISO 105-C10 wash cycles, the treated fabrics still displayed a spray rating of 5/5 and AATCC 193 grade 7, outperforming or equalling the fluorinated control, while causing ≤5% loss of water-vapour permeability and only a marginal increase in bending stiffness. These results demonstrate that the proposed one-step, water-borne sol–gel process affords a sustainable, industrially scalable route to high-performance, durable, water-repellent finishes for both natural and synthetic textiles, offering a viable alternative to PFAS-based chemistry for outdoor apparel and technical applications.