Lithium-air batteries, despite having a superior theoretical performance as compared to other lithium chemistries, demonstrates poor discharge performance. The discharge product in organic electrolyte Li-air cells is lithium peroxide (Li₂O₂), which precipitates as a solid phase during discharge and gives rise to pore network evolution for the porous electrode. To make matters worse, lithium peroxide is electronically insulating and in turn evolves the electrochemically active interface. On the other hand, as dissolved oxygen is consumed during electrochemical discharge, additional oxygen from air is to be transported from ambient to reaction zone. Finite solubility and finite rate oxygen transport may lead to oxygen starvation for faster operation (related with electrolyte phase transport description). The relative severity of these microstructural and electrolyte phase limitations jointly determines the cell performance. Consistent and comprehensive descriptions for microstructural evolution and electrolyte phase transport are developed here, and in turn physicochemical evolution in Li-air cells investigated. Depending on the severity of these resistive modes, different strategies for cell performance improvement are highlighted.