Chemical synthesis and physical blending methods were used to prepare thermal sensitive polyurethanes (TSPU) with single or double thermal switches. In the design of the formula, polycaprolactone diol (PCL) with a molecular weight 10,000 and 4,000 and polytetramethylene glycol (PTMG) with a molecular weight 3,000 and 2,000 were used as the soft segments. The effects of the crystallinity and compatibility of the soft segments on the phase transition temperatures of the soft segments of TSPU (defined as switch temperature, T (s) ) were investigated in detail. To examine the thermal sensitivity of the thermal switch, water vapor permeability (WVP) experiments were performed to investigate the mass transport as a function of temperature. Differential scanning calorimetry (DSC) indicated that all the original TSPUs had a phase separated structure that was independent of the phase transition temperature of the soft and hard segments. The T (s) values are determined mostly by the melting temperatures of the soft segments. On the other hand, for their blends, the T (s) values are determined by the compatibility of the soft segments and the blending weight ratio. The blends of the PCL-based TSPUs showed good compatibility and single T (s) due to the similar structure of the soft segments (just a difference in molecular weight), whereas for the PCL-based and PTMG-based TSPUs (the molecular structure is very different) blends, the T (s) two independent values and blending weight ratio-dependent features due to the difference in the structure of the soft segments. Water vapor permeability analysis revealed the mass transport showed switching features to thermal stimuli, i.e. when the temperature reached the Ts, the WVPs of membranes showed rapid changes. On the other hand, the sensitivity of the thermal switch characterized by WVP improvement showed a dependence on the degree of crystallinity of the soft segments, i.e. well-organized soft segment structure is beneficial for improving the thermal sensitivity. Overall, TSPU membranes with a single T (s) and different thermal sensitivity can be prepared using different crystalline poly-diols as the soft segments and blending two types of TSPUs with similar soft segments in the molecule structure, whereas TSPU with a double T (s) can be achieved easily by blending two types of TSPUs with different soft segments.