Li-O2 batteries offer a high theoretical discharge capacity due to the formation of light discharged species such as Li2O2 which fill the porous positive electrode. However, in practice it is challenging to reach the theoretical capacity and completely utilize the full electrode pore volume during discharge. With the formation of discharge products, the porous medium evolves, and the porosity and tortuosity factor of the positive electrode are altered through shrinkage and clogging of pores. A pore shrinks as solid discharge products accumulate, the pore clogging when it is filled (or when access is blocked). In this study, we investigate the structural evolution of the positive electrode through a combination of experimental and computational techniques. Pulsed-field Gradient Nuclear Magnetic Resonance results show that the electrode tortuosity factor changes much faster than suggested by the Bruggeman relation (an equation that empirically links the tortuosity factor to the porosity), and that the electrolyte solvent affects the tortuosity factor evolution. The latter is ascribed to the different abilities of solvents to dissolve reaction intermediates, which leads to different discharge product particle sizes: on discharging using 0.5 M LiTFSI in dimethoxyethane, the tortuosity factor increases much faster than for discharging in 0.5 M LiTFSI in tetraglyme. The correlation between discharge product size and tortuosity factor is studied using a pore network model which shows that larger discharge products generate more pore clogging. The Knudsen diffusion effect, where collisions of diffusing molecules with pore walls reduce the effective diffusion coefficients, is investigated using a kinetic Monte Carlo model and is found to have an insignificant impact on the effective diffusion coefficient for molecules in pores with diameters above 5 nm, i.e., most of the pores present in the materials investigated here. As a consequence, pore clogging is thought to be the main origin of tortuosity factor evolution.