Novel hydroxyalkyl carbamate, dihydroxyalkyl carbamate terminated poly(dimethylsiloxane) (PDMS) oligomers, and carbamate-linked block copolymers with poly(epsilon-caprolactone) (PCL) were designed, synthesized, and characterized using combinatorial and high-throughput experimentation (CHTE). Novel hydroxyalkyl carbamate terminated PDMS oligomers were synthesized by reacting 3-aminopropyl terminated PDMS oligomers with ethylene carbonate (EC); further reaction of these oligomers with epsilon-caprolactone (epsilon-CL) resulted in novel carbamate-linked PCL-PDMS-PCL triblock copolymers. Novel dihydroxyalkyl carbamate terminated PDMS oligomers were synthesized by reacting 3-aminopropyl terminated PDMS with glycerine carbonate (GC); further reaction of these oligomers with epsilon-CL resulted in novel H-type block copolymers of PDMS and PCL. Structural characterization of the synthesized oligomers and block copolymers was carried out with high-throughput FTIR, DSC, and NMR. Molecular weights of the oligomers and block copolymers were characterized using Rapid GPC.