Conformal poly(cyclohexyl methacrylate) (pCHMA) thin films were synthesized via initiated chemical vapor deposition (iCVD), with tert-butyl peroxybenzoate (TBPOB) as the initiator, representing the first time that TBPOB has been used as an initiator for iCVD synthesis. Using TBPOB instead of tert-butyl peroxide (TBPO), the rate of iCVD film growth increased by a factor of up to seven at comparable conformality and lower the filament temperature from 257 to 170 °C at a comparable deposition rate of 3 nm/min. The conformal deposition of functional thin films is desired for applications including microfluidics, medical devices and membranes. Lower filament temperatures reduce the heat load to the deposition surface and thus are advantageous for polymeric substrates that are temperature sensitive or monomers that decompose at high temperatures. Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) results demonstrate the similarity of the TBPOB- to the TBPO-initiated pCHMA main chains. However, the aromatic group in TBPOB provided a unique spectral signature of the polymer chain end group in the FTIR and the peak intensity increased with increase of filament temperature. Scanning electron micrographs (SEMs) revealed that the pCHMA coatings are conformal over non-planar structures; however, at identical process conditions, TBPO-initiated films showed a slightly better conformality due to the lower sticking coefficient of TBPO. At a monomer partial pressure of 0.45, TBPOB has a sticking coefficient value of 0.1188 ± 0.0092, which is ∼3 times as high as that of TBPO (0.0413 ± 0.0058). The step coverage is insensitive to filament temperature if the surface concentration of the monomer is fixed.