The synthesis of high‐molar‐mass first‐ and second‐generation, aromatic sulfonamide‐based dendronized polymers PG1(CH3) and PG1(NO2) as well as PG2(CH3) and PG2(NO2) has been achieved. For PG3(CH3) at least oligomeric material could be obtained. The polymers exhibit glass transition temperatures in the range of 135–162 °C and are valuable components for a presently ongoing in depth analysis of the persistence length of dendronized polymers by SANS. The corresponding monomers MG2(CH3) and MG2(NO2) were crystallized and their structures in the crystal determined by XRD. These single crystals are the first ever obtained of dendritic macromonomers. The polymerizable units were found not to be in a proper spatial relation to allow for a solid‐state polymerization.