Aligned multi-walled carbon nanotubes (MWCNTs) were produced with different diameters, according to the thickness of Ni catalyst layer, by microwave plasmas enhanced chemical vapor deposition, in N2/H2/CH4 environment. Raman spectroscopy, performed both on top and lateral surfaces, revealed that the relative intensity of the G′ band and the G and G′ bandwidths have high sensitivity to tube diameter distribution and also to structural variations along the tube axis. The D band present a distinct behavior: ID/IG is sensitive to structural organization, particularly along tube axis, while D bandwidth is sensitive to tube diameter distribution. This result may indicate D bandwidth as a parameter to correlate to the diameter of the aligned MWCNTs.