Though defects are invariably present in as-grown and purified carbon nanotubes (NTs), spectroscopic properties of defects in NTs have not been established yet. In this work, single walled (SW) and multiwalled (MW) carbon nanotubes (NTs) grown by chemical vapor deposition have been studied by high resolution transmission electron microscopy (HRTEM), Raman scattering and photoluminescence (PL), electron spin resonance (ESR) and thermo gravometric (TGA) analysis. Raman spectra of both SWNT and MWNT show additional features in the frequency range intermediate between 600–1300 cm−1 and 1700–2600 cm−1, in addition to well-known radial breathing modes, D- and G-bands. Room temperature PL studies show two broad but distinct peaks centered at ∼2.05 eV and ∼2.33 eV, for both SWNT and MWNT samples. TGA analysis shows very low impurity content in MWNT sample as compared to the SWNT sample. HRTEM analysis reveals various kinds of structural defects in nanotube wall. With the help of HRTEM and ESR studies, we argue that the intermediate frequency Raman modes and the visible PL from the pristine NTs are definite signatures of structural defects in the nanotubes.