There have been health concerns raised against the use of gadolinium (Gd)-based magnetic resonance imaging contrast agents. The primary observation is that Gd ions are prone to leaking into the bloodstream, causing nephrogenic systemic fibrosis as one of the side effects. In addition, such leakage of the ions inhibits easy clearance from the body. Herein we propose that Gd-ascorbate nanoparticles could be one of the safer choices as they are rather stable in aqueous dispersion and they do not get affected by Zn or Fe ions in the medium. The magnetic properties of the ions are preserved in the nanoparticles, and particles when sufficiently small may be amenable to renal clearance from the human body. Thus, when an aqueous solution of Gd-acetate and ascorbic acid was left to evolve with time, a Gd-ascorbate complex was formed that led to the formation of nanoparticles with time. The sizes of the nanoparticles increased with time, and when the particles were sufficiently large, they precipitated out of the medium. In addition, smaller nanoparticles were consistently present at all times of observations. UV-vis, photoluminescence and FTIR spectroscopy, mass spectrometry, and transmission electron microscopy analyses confirmed the formation of nanoparticles of Gd-ascorbate complex. In addition, magnetic measurements confirmed the high relaxivity of the nanoparticles as compared to the parent salt, indicating the effectiveness of the nanoparticles as contrast agents. Density functional theory-based calculations of the molecular complex-based nanoparticles accounted for the experimental observations.