A family of smectic liquid‐crystalline dendrimers has been synthesized by connecting rodlike cyanobiphenyl mesogens, with various spacer lengths, at the periphery of poly(propylene imine) dendrimers. A combination of differential scanning calorimetry, optical microscopy, and X‐ray diffraction suggests that, under the influence of the mesogenic endgroups, the dendrimer has to adopt a highly distorted conformation.