Novel polycyclic siloxane resins were prepared from phenol-formaldehyde novolac type resins by reacting them with dialkyl or diaryl dichlorosilanes under anhydrous and high dilution conditions. The formation of polycyclic species was confirmed by the detection of absolute masses by MALDI-TOF mass spectrometry. H-1- and Si-29-NMR confirmed the substitutions of phenolic hydroxy groups by siloxane bonds. Curing studies were conducted on the polycyclic siloxane resins as well as on the polycyclic siloxane resins incorporated into two types of polysiloxane gums. A trace amount of potassium hydroxide was used as a catalyst for the crosslinking of these systems. The blend of polysiloxane with 30 wt % polycyclic siloxane was found to be stable at the curing temperature. Differential scanning calorimetry and thermogravimetric analysis techniques were used to study the thermal profiles of these systems.