The utilization of hydroxypropyl cellulose (HPC) can be regarded as unexpected with regard to certain applications, such as being employed as a solubility enhancer for poorly soluble drugs and as a solubilizing agent for nano‐suspensions and amorphous solid dispersions. However, the best results were obtained for low‐molecular weight (Mw) HPC grades with a short‐chain structure. Therefore, in this study, seven grades of HPC with different polymer chain lengths (Mw) are analyzed in various aqueous solutions by a combination of 1H quantitative NMR spectroscopy, diffusion NMR spectroscopy, and water ligand observed via gradient spectroscopy; these investigations provide insights into the remarkable solubilizing property of HPC at the molecular and supramolecular levels. Furthermore, the hydration and the water residence time are found to be strongly dependent on the polymer chain length of HPC. The quantitative results obtained herein indicate that HPCs with shorter chain lengths retain smaller amounts of water around their hydrated molecules, as compared to their counterparts with longer chain lengths.