Branched glycerol dialkyl glycerol tetraether (GDGTs) membrane lipids have been used as a new proxy for the reconstruction of terrestrial palaeoclimates. These biomarkers (or molecular ‗fossils‘) in conjunction with palynology, have been effective in the novel analysis of Miocene organic-rich sediments from three South African west coast sites at Rondeberg, Noordhoek and Langebaanweg. Lastly, a Quaternary south coast site at Rietvlei, South Africa, was also studied to further elucidate the extent of use of this new proxy. The fluvial peat and organic-rich deposits of the Elandsfontyn Formation (Sandveld Group) were investigated at Noordhoek, Langebaanweg and Rondeberg to provide new evidence for the climate and vegetation patterns during Miocene in this region. Drill-core and quarry samples from all four sites were freeze-dried, powered, and prepared for biogeochemical and palynological analyses. The methylation index of branched tetraethers (MBT) and cyclisation ratio of branched tetraethers (CBT) proxies were used to calculate the mean annual air temperature (MAAT) and pH values of the organic-rich horizons at time of deposition. The Branched versus isoprenoid index of tetraethers (BIT) was used to assess the relative contributions of marine archaeal and terrestrial bacterial tetraethers, and thereby assess the validity of the MBT, CBT and calculated palaeoenvironmental factors. The results presented in this thesis suggest that the use of the MBT/CBT proxy has significant potential in southern Africa, and may complement previously attempted palaeoclimatic and palaeoecological studies of Neogene-aged South African sediments. This type of research has the capacity to provide palaeoenvironmental information where other proxies may be absent. Results indicate that all sites yielded branched tetraether membrane lipids with the exception of Rondeberg, where GDGTs were below detection as a result of poor preservation conditions. Palynological investigation confirmed proxy derived temperatures. Furthermore palynomorph analyses supplemented earlier studies of the Noordhoek site and were piloted for the Rondeberg site, reaffirming alternating sequences of tropical and subtropical palynofloras. The MAATs, likewise, show variability and pronounced trends through time at the Langebaanweg and Noordhoek sites, generally corresponding with the variation and diversity of the pollen population. The terrestrial MAAT results appear to compliment Southern Hemisphere sea level changes associated with Antarctic glaciations. Additionally, this data shows a pattern similar to the Southern and Northern Hemisphere marine isotope records of relative fluctuations in the global climate and sea level change from the early to middle Miocene. The application of these past climate change indicators have been proved to be useful in the reconstruction of South Africa Miocene palaeoclimates, and may aid in understanding the consequences of climate change in the Cape region.