The analysis of the sea-ice diatom biomarker IP25 (a mono-unsaturated Highly Branched Isoprenoid (HBI) alkene) in Arctic marine sediments has previously been shown to provide a useful qualitative proxy measure for the past spring sea-ice occurrence. In the Southern Ocean the occurrence and variable abundance of a structurally similar di-unsaturated HBI (HBI diene II) has previously been proposed as a proxy measure of paleo sea-ice extent. However, the use of such biomarker proxies remains under development. In the current study, a number of additional palaeoceanographic developments of HBIs as sea-ice biomarkers in both polar regions has been undertaken. For the Arctic, an investigation into the combined analysis of IP25 and certain phytoplankton biomarkers has been conducted with the aim of providing more detailed and semi-quantitative descriptions of sea-ice conditions in the Barents Sea. In contrast, analysis of HBIs and other lipids within water column, surface sediment and sea-ice samples has been undertaken to provide further insights into the use of HBIs as proxies for Antarctic sea-ice. Analysis of surface sediments from across the Barents Sea has shown that the relative abundances of IP25 and a tri-unsaturated HBI lipid (HBI triene IIIa) are characteristic of the overlying surface oceanographic conditions, most notably, the location of the seasonal sea-ice edge. A semi-quantitative approach, in the form of the PIP25 index, showed a good positive linear relationship between PIP25 indices and spring sea-ice concentration, with a particularly strong relationship found when using HBI triene IIIa (PIIIaIP25) as the open-water counterpart to IP25. The quality of the linear fits were not especially dependent on the balance factor c, used in the PIP25 calculation, which may have important positive consequences for down-core sea-ice reconstruction, and when making comparisons between outcomes from different Arctic regions or climatic epochs. Further, a lower limit threshold for PIIIaIP25 (0.8) might represent a useful qualitative proxy for the past occurrence of summer sea-ice. The re-evaluation of biomarker data from three dated marine sequences in the Barents Sea suggests that the combined analysis of IP25 and HBI triene IIIa can provide information on temporal variations in the position of the maximum (winter) Arctic sea-ice extent, together with more quantitative sea-ice reconstructions. In the Southern Ocean, the distributions of di- and tri-unsaturated HBIs (HBI diene II and HBI trienes IIIa and IIIb) in surface waters were shown to be extremely sensitive to the local sea-ice conditions, consistent with significant environmental control over their biosynthesis by sea-ice diatoms and open water phytoplankton, respectively. Within the water column, the apparent alteration to HBI and other lipid abundances was evident between the photic and benthic parts of the water column, which, along with additional local factors (e.g. polynya formation), may have important implications for paleo sea-ice reconstructions. The sedimentary occurrence and distribution of HBI diene II (termed here as IPSO25) were consistent with the recent identification of the diatom Berkeleya adeliensis Medlin as a source of IPSO25. The tendency for B. adeliensis to flourish in platelet ice, the formation of which is strongly associated with super-cooled freshwater inflow, means that sedimentary IPSO25 may provide a potentially sensitive proxy indicator of landfast sea-ice influenced by meltwater discharge from nearby glaciers and ice shelves. Re-examination of some previous IPSO25 down-core records supports this suggestion, although further down-core analysis is required to confirm this hypothesis. The similar sedimentary distribution relationship between phytoplankton-derived HBI trienes and IPSO25, further indicates that the former may reflect production of these biomarkers by certain diatoms that flourish within the region of the retreating ice edge; however, the source identification of the HBI trienes is still needed to place this interpretation on a firmer footing.