Aiming to better understand the biomass pyrolysis and gasification processes, a detailed experimental study of the mixing characteristics is conducted in a fluidized bed with binary mixtures. Rapeseed is used as biomass, and silica sand or resin as inert material. The effect of mixture composition, initial packing manner, and superficial gas velocity on the concentration distribution is investigated in a rectangular fluidized bed by means of photography and sampling methods. The results show that the mixture composition plays an important role in the axial solids profile of binary mixtures. The mixing behavior of binary mixture is dominated by the bubble movement. The axial distribution of binary mixtures becomes uniform with increasing superficial gas velocity, whilst no obvious effect of initial packing manner is observed in this study.