The miscibility between two gels with largely different gelation behaviors is an interesting topic both scientifically and practically. This paper reports a novel bi-phasic system based on two natural polymers, hydroxypropyl methylcellulose (HPMC) which has a thermal gelation behavior, and hydroxypropyl starch (HPS) which has a cooling gelation property. While both biopolymers have the same glucose unit grafted with propylene oxide, and are compatible to a certain degree, they were observed immiscible because of their different gelation behaviors. The immiscibility of these two compatible polymers could result in special structures leading to different blend film properties. Regarding this, the morphology, thermal transition, mechanical properties and oxygen barrier property could be well tailored by the ratio of two biopolymers and the environmental conditions. The knowledge obtained from this work could be useful for understanding other similar systems with desirable structure and properties
