Convergent and divergent syntheses of novel organic hybrid structures termed dendron rodcoils (DRC) containing dendritic, rodlike, and coillike segments are described. The aryl ester dendron masked with 32 trifluoromethyl groups is prepared via a convergent approach using 5-(tert-butyldimethylsiloxy)isophthalic acid as the monomer unit. The activation of the focal point of the dendron allows for successful coupling between the dendron and the diblock rodcoil molecules synthesized separately. In another example, the dendritic block is grown via divergent strategy from the terminus of rodcoil using 3,5-bis(tert-butyldimethylsiloxy)benzoic acid as an AB(2) Monomer. A combination of catalyzed esterification reactions and silyl deprotection chemistry proved to be a very efficient method for construction of these nanosized structures with unusual molecular architecture. Both synthetic strategies allowed for the preparation of DRCs with nearly monodisperse dendritic blocks as demonstrated by NMR, MALDI-TOF, and GPC measurements.