Differences in chemical weathering extent and character are expected to exist across topographic escarpments due to spatial gradients of climatic and/or tectonic forcing. The passive margin escarpment of south-eastern Australia has a debated but generally accepted model of propagation in which it retreated (within 40 Ma) to near its current position following rifting between Australia and New Zealand 85–100 Ma before present. We focus on this escarpment to quantify chemical weathering rates and processes and how they may provide insight into scarp evolution and retreat. We compare chemical weathering extents and rates above and below the escarpment using a mass balance approach coupling major and trace element analyses with previous measurements of denudation rates using cosmogenic nuclides (10Be and 26Al). We find a slight gradient in saprolite chemical weathering rate as a percentage of total weathering rate across the escarpment. The lowlands area, encompassing the region extending from the base of the escarpment to the coast, experiences a greater extent of chemical weathering than the highland region above the escarpment. Percents of denudation attributable to saprolite weathering average 57 ± 6% and 47 ± 7% at low and high sites respectively. Furthermore, the chemical index of alteration (CIA), a ratio of immobile to mobile oxides in granitic material that increases with weathering extent, have corresponding average values of 73·7 ± 3·9 and 65·5 ± 3·4, indicating lower extents of weathering above the escarpment. Finally, we quantify variations in the rates and extent of chemical weathering at the hillslope scale across the escarpment to suggest new insight into how climate differences and hillslope topography help drive landscape evolution, potentially overprinting longer term tectonic forcing. Copyright © 2009 John Wiley & Sons, Ltd.