Aims. We aim to present 70 spectra of 68 new high-redshift type Ia supernovae (SNe Ia) measured at ESO's VLT during the final two years of operation (2006-2008) of the Supernova Legacy Survey (SNLS). This new sample complements the VLT three year spectral set. Altogether, these two data sets form the five year sample of SNLS SN Ia spectra measured at the VLT on which the final SNLS cosmological analysis will partly be based. In the redshift range considered, this sample is unique in terms of homogeneity and number of spectra. We use it to investigate the possibility of a spectral evolution of SNe Ia populations with redshift as well as SNe Ia spectral properties as a function of lightcurve fit parameters and the mass of the host-galaxy. Met...