New dendrons and dendrimers with dendritic arms composed of alternate phenyleneethynyleneand phenylenevinylene moieties have been efficiently synthesized using orthogonal and convergentsyntheses that combine Sonogashira and Horner−Wadsworth−Emmons reactions. Two differentiterative routes have been developed that allow specific control over the placement of double andtriple bonds within the interior of the dendrimers. A preliminary study of the UV and photoluminescence (PL) properties of the resulting compounds is also described. All of the examplesprepared are blue-luminescent.