Australia has likely the world's highest residential photovoltaic (PV) system penetration. In this paper, the impact of distributed PV on peak demand at different distribution network zone substations (ZSs) is assessed by upscaling 15 min PV generation data from 270 distributed PV systems across Sydney, Australia, and comparing it with load data from 138 ZS serving the Sydney region. Gross load (load had there been no PV) was estimated, allowing the impact of current and higher PV penetrations on the value and time of peak at the different ZSs to be assessed. A probabilistic assessment of the impact of PV on ZSs is conducted, based on the availability of PV during the peak demand periods. To better understand the impact of PV on peak demand, K-means clustering is used to group ZSs based on PV generation during peak periods as the clustering features. Mapping of PV availability across percentage of peak times for all ZSs highlights the interannual variability of peak reductions and the potential impact of short-term load shifting. The impact of different penetration levels of distributed PV on the peak demand of the entire distribution network is also assessed by aggregating the ZS loads.