Yearly, thousands of tons of wasted coffee grounds are produced according to high coffee consumption. Still, after the coffee brewing, wasted coffee grounds contain some amounts of caffeine (CAF). CAF, in turn, contains multiple O and N chelating atoms in its structure. These have a potential to be reductors for complexes of metals. In this context, within the present study, a set of CAF extracts derived from coffee beans and coffee grounds were obtained and then used for the one-step reduction of ReO ions with no additional toxic chemicals. Within this approach, CAF was applied as a secondary, green resource for the synthesis of unique rhenium nanoparticles (ReNPs) containing Re species at 0 and +6 oxidation states. The obtained ReNPs were identified and characterized with the use of X-ray powder diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). Further, the capping and stabilization of ReNPs by CAF were verified with the aid of Fourier transformation infrared spectroscopy (FT-IR). The so-obtained "green" ReNPs were then used as a homogenous catalyst in the catalytic hydrogenation of 4-nitrophenol (4-NP). This new nanomaterial revealed a superior catalytic activity, leading to the complete reduction of 4-NP to 4-aminophenol within 40-60 min with a first-order rate constant of 0.255 min.