Particle size polydispersity considerably influences the chemical looping combustion (CLC) of solid fuels. In the present work, a three-dimensional multiphase particle-in-cell (MP-PIC) method was established and applied to study the full-loop CLC of biomass under a continuous injection mode. After model validation, the gas–solid flow characteristics, solid circulation rate (SCR), particle mixing in a fuel reactor (FR), and biomass leakage at different oxygen carrier (OC) particle size distribution (PSD) widths and biomass densities were systematically explored. The results showed that OC particles significantly stratified within the FR and both loop seals. Moreover, the fluctuation amplitude of the SCR decreased as the OC PSD width increased. Small biomass particles were more likely to leak. The number fraction of total leaked biomass particles first decreased and then increased as the OC PSD width increased. In the FR, small OC particles were primarily distributed in the upper part of the bed, and large particles were mainly distributed in the lower part. In addition, within the test range, the magnitude of the density difference between biomass and OC particles positively correlated with the likelihood of biomass leaking. These observations are all beneficial for the design and optimization of the CLC process of biomass.