The structural features of chars derived from pyrolysis of mallee wood of different particle sizes in a novel fluidized-bed/fixed-bed reactor have been investigated. Raman spectroscopy was used for structural evaluation of chars. Spectra were curve-fitted with 10 Gaussian bands representing typical structural features of the chars. The temperature had a significant influence on the evolution of char structure and thus the total Raman peak area between 800 and 1800 cma?? 1 is seen to decrease significantly with increasing pyrolysis temperature for all chars. On the other hand, the ratio ID/I(Gr + Vl + Vr) between the band intensities of condensed aromatic ring systems (> 6 rings) and amorphous char structures with small aromatic ring (3a??5 rings) systems is seen to increase with increasing temperature. The particle size of biomass has a great role in char structure at fast heating rate (> 1000 A?C/s) pyrolysis although it has no effect on char structure at slow heating rate pyrolysis (0.17 A?C/s). However, in the bigger biomass particle, the structure of char prepared under fast heating rate pyrolysis is similar to that of the structure of char prepared under slow heating rate pyrolysis.