Dipodal silanes possess two silicon atoms that can covalently bond to a surface. They offer a distinctive advantage over conventional silanes in terms of maintaining the integrity of surface coatings, adhesive primers and composites in aqueous and aggressive environments. The improved durability of such dipodal silanes is associated with an increased crosslink density of the interphase and the inherent resistance to hydrolysis, as they can form six, rather than three, Si-O bonds to the substrate. This study examines dipodal silanes with hydrophobic alkyl functionality and compares them with similar functionality on conventional silane coupling agents. It also introduces new structural dipodal silanes containing “pendant” and “bridged” functionality and then examines their stability in aqueous environments. In strongly acidic and brine environments, dipodal silanes clearly demonstrate improved resistance to hydrolysis compared to conventional silane coupling agents.