To understand the complex nanoscale dehydration process during the lower critical solution temperature (LCST) based inverse phase transition of a class of thermoresponsive biopolymers, diblock elastin-like polypetides (ELPs) were investigated by spin probing continuous wave electron paramagnetic resonance (CW EPR) spectroscopy. The diblock copolymers composed of a hydrophobic block and a hydrophilic block showed different mechanisms of a temperature-driven phase transition. While the phase transition temperature is a function of the hydrophobic mass fraction of the diblock ELPs, the hydrophilic block length determines the molecular structure of the polymer aggregates formed above the transition temperature. When the weight ratio of hydrophilic block length to hydrophobic block length is greater than or equal to 0.3, the polymer aggregates consist of a hydrophobic core and a hydrophilic corona. The interface of these two regions become permeable at temperatures above the transition temperature. In case of smaller ratios, the aggregating hydrophobic parts of the polymer enclose the hydrated hydrophilic blocks, that are too small to form a hydrophilic corona, leading to bigger and less dense aggregates of higher polarity.