This investigation focused on the self-assembly of poly(N-isopropylacrylamide)-block-poly(ethylene glycol) (PNIPA-block-PEG) in water. A quasi-living radical polymerization technique including a Ce(IV) ion redox system enabled us to prepare block copolymers with relatively narrow molecular weight distributions. We distinguish five regions in the phase diagram: a transparent sol, opaque sol, transparent gel, opaque gel, and syneresis. By examining the extent of changes in the spectroscopic properties of a fluorescence probe, pyrene, as a function of block polymer concentration and/or temperature, we determined the critical association concentration as well as the partition coefficient K, for pyrene. The spectroscopic properties indicate that the hydrophobicity around the probe starts to increase far below the demixing line of the PNIPA-block-PEG, a remarkable finding which suggests that even in the temperature region below the LCST temperature of a PNIPA block (similar to 32 degrees C), this block copolymer provides more space for a preferential transfer of pyrene molecules than a bulk water medium at a higher temperature. This result may be attributed to the action of water, which starts to behave as a selective solvent for PEG blocks; the PEG chains are more swollen with water than are the PNIPA chains. Dynamic light scattering measurements also indicate that contraction of the PNIPA block starts to occur around 18 degrees C, which is consistent with results obtained by fluorescence measurements. By employing small-angle neutron scattering, it is also confirmed that microphase separation occurs above 17 degrees C to form disordered micelles, which includes a range of states from W asymmetric swelling to (ii) micelle formation with only short-range liquidlike order. Above 30 degrees C, network domains are formed as a result of macrophase separation due to dehydration of PNIPA blocks. As the temperature increased up to 40 degrees C, the network domain is collapsed along a direction parallel to PNIPA-block-PEG interface, leading to increase in interfacial thickness and to macroscopic syneresis.