Low complexity and efficient algorithms for Radio-Frequency Identification (RFID) are crucial to foster low-cost and energy-saving solutions. With the aim of lowering the complexity of the radio circuitry, and inspired by the superposition codes concept, we propose a novel encoding algorithm for tag-to-reader communication channels of modern RFID systems. We show that the developed scheme-despite the simplicity of its hardware realization-allows a coding gain comparable to the one obtained by the more complex Viterbi decoding of the Miller 4 modulation scheme used in the EPC Generation 2 Class 1 RFID standard. Simulation results prove the effectiveness of the proposed solution for low-cost tags, under different signal-to-noise ratios (SNRs) and interrogation time durations. Although our numerical evaluation mainly focuses on the EPC Generation-2 standard, we believe that the proposed scheme will also be attractive for future Ultra-wideband RFID systems.