This paper points out the viability of the utilization of metamaterial transmission lines as a multifrequency impedance matching network, improving RF-Energy Harvesting systems operating around 2.4 GHz and 5 GHz. Metamaterial transmission lines introduce additional degrees of freedom in the transmission line design, providing the possibility to match the impedance in multiple bands. The impedance matching structure has been designed and optimized using ADS simulator to match the input impedance of a four-diode-bridge rectifier connected to an energy management system. The proposed Metamaterial Impedance Matching Network (MIMN) has been fabricated using standard PCB technologies and tested in a full operative ambient RF-Energy Harvesting System obtaining a DC output voltage of 1.8 V in a 6.8 mF supercapacitor.