A review with 14 references on the synthesis, crystalline structure, liquid crystallinity, melt rheological behavior, gas separation and pervaporation properties of a new type of functional liquid crystalline polymer polyphosphazene is presented. The effect of the side groups of the polyphos phazene on the crystalline structure, liquid crystallinity and gas separation properties is discussed. It is suggested that the polyphosphazene membrane exhibits good gas separation and organic aqueous pervaporation capabilities.