The boron content and isotopic composition (δ11B) of marine carbonate organisms can be linked to the pH of the seawater in which they have grown, making carbonates a useful tool for palaeo-seawater pH reconstruction. A study by Furst (1981) documented unusually high boron concentrations in siliceous sponge spicules, in range from hundreds to a thousand ppm. This observation and the potential for preferential incorporation of the tetrahedral borate species into biogenic silica raises the question as to whether the boron chemistry of biogenic silica might also be influenced by seawater pH. We have measured the boron concentration and isotopic composition of siliceous sponges from the Southern Ocean region, with a view to (1) confirming the observations of Furst (1981), (2) assessing the factors that control boron incorporation and isotopic compositions of sponge silica, and (3) investigating the potentially significant role of siliceous sponges in the marine boron cycle. The measured boron concentrations in a diverse range of both demosponge and hexactinellid sponges confirm the high boron concentrations previously reported. The boron isotope compositions of these sponges vary from around +2‰ to +25‰ and greatly exceed the range in marine carbonates. This isotopic variation is inconsistent with seawater pH control but is correlated with ambient seawater silicon concentration, in a manner that suggests a link to silicon uptake kinetics and demand by sponges.