We have developed a novel approach for forming dendrimer monolayers. A Lys-Lys-Glu tripeptide with a dioctadecylamino tail at the C-terminal and an acetyl head at the N-terminal was newly synthesized as a unit. Three generations of the dendrimers were successfully synthesized by stepwise deprotection and condensation. The molecular area in the condensed phase of all the dendrimers was comparable to the total area of the alkyl chain cross section, but the packing behavior somewhat depends on the generation number. This method will provide a well-defined two-dimensional arrangement of the hydrophobic tails and polar heads with desirable sequences and combinations.