A new organic precursor was designed and synthesized in order to form polymer films having low dielectric constants by a plasma-enhanced co-polymerization (PCP) technology. The organic monomer features a large aliphatic hydrocarbon structure, tricyclodecane (TCD) group. Optimized polymer films deposited from the monomer had dielectric constants less than 2.5. A solid 13C-NMR spectrum showed that the TCD moiety in the precursor was included in the polymer without changing the structure. The effect of the deposition temperature on the film structure was studied by analyzing Raman spectra. It was revealed that the dielectric constant is strongly associated with sp2 carbon content in the TCD-based polymer films.