Two DendriMac polymers (Dendri‐hydr and Dendri‐click) are efficiently and conveniently synthesized via the combination of living anionic polymerization (LAP) and hydrosilylation/click chemistry. Based on the end‐capping of DPE derivatives (DPE‐SiH and DPE‐DA) toward polymeric anions, the polymeric core and arms are effectively synthesized, and the base polymers can be regarded as polymeric bricks. Hydrosilylation and click chemistry are used as coupling reactions to construct the DendriMac polymers with high efficiency and convenience. The numbers of branched arms are calculated by SEC as 5.84 and 6.08 for Dendri‐hydr and Dendri‐click, respectively, which indicate that the DendriMac architectures exhibit high structural integrity. Because of its independence, high efficiency, and convenience, the whole construction can be regarded as the “building of polymeric bricks.”
