In this study, an efficient, stable, and reusable hydrogen-releasing Polyvinylpyrrolidone (PVP) modified PtRh nanoparticles were synthesized and used in the dehydrogenation of dimethylamine borane (DMAB), which is a safe and suitable hydrogen transporter for batteries, and fuel at ambient conditions. The PVP modified PtRh nanoparticles showed high catalytic activity in this reaction and its characterization was performed by TEM and XRD techniques. The characterization studies have shown that the PVP modified PtRh nanoparticles have a particle size of 2.491 ± 0.808 nm. The PVP-modified PtRh nanoparticles have been tested in various parameters such as temperature, substrate, and catalyst concentrations. The experiments showed that the catalytic activity of the PVP modified PtRh nanocatalyst in the dehydrogenation of DMAB under ambient conditions is quite high (TOF = 544.821 h−1). In addition, the activation energy for the catalytic dehydrogenation reaction of dimethylamine borane was calculated as Ea = 23.51 kJ.mol−1. Besides, to accurately predict the catalytic activity, the artificial neural networks (ANNs) model was developed. It was obtained the optimum condition predicted by the ANN model, concentration of PVP modified PtRh nanocatalyst = 9.00 mM, DMAB concentration effect of 137.2 mM, and temperature of 32.6 °C which in this case catalytic activity was obtained (TOF = 561.173 h-1).