Structure-property relations in polydimethylsiloxane (PDMS) containing segmented copolymers with model hard segments capable of forming hydrogen bonding, such as urea, N-methylurea and urethane have been investigated. High molecular weight silicone containing copolymers with these hard segments were prepared from PDMS oligomers with number average molecular weights ranging from 890 to 3750 g/mol. Due to major differences in the solubility parameters between PDMS and polar hard segments, all copolymers are expected to display good microphase separation. It was demonstrated that mechanical and thermal properties of these copolymers are directly linked to the strength of the hydrogen bonding in the hard segments. As expected, siloxane-urea copolymers displayed much higher tensile strengths when compared with siloxane-N-methylurea and siloxane-urethane copolymers with similar compositions.