Double-walled carbon nanotubes (DWCNTs) synthesized by catalytic chemical vapor deposition (CCVD) have been functionalized by bromine vapor at room temperature. At least two different bromine species were detected in the product using X-ray photoelectron spectroscopy (XPS) and thermal gravimetric analysis. The primary form is negatively charged Br2 molecules exhibiting an intense resonance at ∼238 cm−1 in the Raman spectrum. The electron transfer from the nanotubes to the adsorbed molecules is detected from C 1s XPS and near-edge X-ray absorption fine structure spectra. The optical absorption spectra reveal that although the metallic nanotubes are more reactive to Br2, the outer semiconducting nanotubes also readily interact with Br2 adsorbates. The secondary bromine form is attributed to covalent C-Br bonding, and its possible sources are discussed in the light of quantum-chemical calculations. Analysis of the XPS, Raman, and optical absorption spectra of the Br-DWCNTs annealed at 100-170 ° C indicates preservation of a part of bromine molecules in samples that affects the electronic and vibration properties of nanotubes.