The layer-by-layer incorporation of monomers in the synthesis of dendrimers allows for variations in the functionalities between one layer and the next. However, incorporation of different functionalities in combination with the above would lead to the introduction of sequences in dendrimers. We review the three complementary synthetic methods we have developed for sequencing the dendrimers. We also illustrate the utility of these methodologies in identifying certain fundamental properties of dendrimers. More specifically, we have probed the intermediate layers of the dendrimers by incorporation of spectroscopic probes in precise locations within dendrimers. Similarly, we have utilized this method to identify the true architectural advantages of dendrimers as light harvesters in solar energy applications.