Reaction of condensation of norbornene and its methyl-subsituted derivative with cyclopentadiene with using dimer of the latter as an initial  component in the presence of the nano-TiO₂ (20 nm) have been studied, as a result, corresponding unsaturated polycyclic hydrocarbons – tetracyclo[4.4.1^2.5.1^7.10.0^1.6]dodec-3-ene and its 8-methyl substituted derivative have been synthesized.