Toluene, carbon tetrachloride, and tetrahydrofuran sorption and desorption by polypropylene (PP and PP/thermotropic liquid crystal polymer (Rodrun) blends with 20 and 40% Rodrun contents were studied as well as the effects of the solvent presence on the structure and mechanical properties. The rate of sorption and desorption and the solvent content at the equilibrium were higher in the blends than in pure PP. This was attributed to microcracking in the PP matrix induced by the presence of Rodrun. Taking into account the very low permeability of Rodrun to the solvents of this work, and the increase in specific volume of the blends as a result of sorption, sorption-induced additional microcracking, partially in the form of debonding of the dispersed Rodrun phase, is also believed to occur. Plasticization was the main effect on mechanical properties. The partially irreversible effect of sorption on the mechanical properties agrees with the proposed partial debonding and weak solvent resistance of these blends.