Post-synthesis modification of polymers is a synthetically appealing approach to generate a range of samples from a single, well-characterised starting material. When partial or mixed-functionalisation is sought, an inevitable statistical distribution of modification outcomes will lead to considerable variation of chemical structures within the final sample. Here we have comprehensively investigated the postsynthesis sequential/partial and simultaneous mixed modification of xanthate-functional ideal dendrons and used this data to consider the implications for the more complex linear-dendritic hybrids and hyper-branched- polydendron analogues. Although H-1 NMR confirmed the potential to direct the reactions, it was clear from MALDI-TOF studies that very little of the actual targeted structures were generated in the statistical reactions.