Understanding the process of self-organization of Ge nanostructures on Si with controlled size distribution is a key requirement for their application to devices. In this study, we investigate the temporal evolution of self-assembled islands during the low pressure chemical vapour deposition (LPCVD) of Ge on Si at 650°C using high growth rates (6–9 nm/min). The islands were characterized by atomic force microscopy, transmission electron microscopy, Rutherford backscattering spectrometry and micro-Raman spectroscopy. We found that the first nanostructures to assemble were small islands, with a narrow size distribution, typical of the ‘lens-shaped’ structures reported in previous studies. Next to form were a population of larger ‘lens-shaped’ islands with a similar surface density to that of the small islands, but with broad height and width distributions. These islands differ from the pyramid-shaped islands previously reported for a similar size range. On further Ge deposition, the population evolves into one of large square-based truncated pyramids with a very narrow size distribution. Such pyramidal structures were previously reported at smaller sizes. Furthermore, we see no evidence of the multifaceted domes previously reported in this size range. The small ‘lens-shaped’ islands appear to be strained, whilst some of the intermediate-sized islands and all the large truncated pyramids contain misfit strain relaxation induced defects. Additionally, in the both the intermediate size ‘lens-shaped’ islands and in the large size truncated pyramidal islands, there is evidence of Si-Ge strain-induced alloying, more significant in the first than in the latter. Our observation of ‘lens shaped’ islands and truncated pyramids at larger sizes than are normally observed, suggests a kinetically driven process that delays the evolution of energetically favourable island structures until larger island sizes are reached.