The effects of temperature, polymer composition, and concentration on the micellization and gelation properties of poly(ethylene oxide) -poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) block copolymers in aqueous solutions were investigated by H-1 NMR spectroscopy. It was found that the temperature-dependent behavior of PPO blocks, observed as changes in chemical shift, half-height width, and integral value, could be attributed as an intrinsic tool to characterize the transition states during unimer to micelle formation. The H-1 NMR spectral analysis revealed that the hydrophobic part, PPO, of the Pluronic polymers plays a more significant role in the temperature-induced micellization, whereas the transitional behavior of Pluronic polymer, i.e., from micellization to liquid crystals formation, resulted in the drastic broadening of the spectral signals for the PEO, indicating that the PEO segments play a more significant role in the crystallization process. It was also observed that the temperature-dependent changes in the half-height width of the PEO -CH2-signal are sensitive to the liquid crystalline phase formation, which could be attributed to the close packing of spherical micelles at high polymer concentrations or temperatures.