We report the synthesis and uses of a novel terpyridine-functionalized chain transfer agent (CTA) that produces well-controlled macromolecular architectures with terpyridine functionalities at one chain end via reversible addition-fragmentation chain transfer (RAFT) polymerization. The terpyridine-terminated macromolecules with well-defined structures were further used for preparation of supramolecular diblock metallomacromolecules by bis(2,2':6',2"-terpyridine)ruthenium(II) complex connectivity. The successful connectivity between two macromolecular blocks via the metallocomplex was confirmed by UV-vis, size exclusion chromatography (SEC), and differential scanning calorimetry (DSC) as well as atomic force microscopy (AFM) techniques.