An appropriate pulse-coding algorithm is the key to achieving an efficient switched-mode power amplification in all-digital transmitters. A five-level RF-PWM method with third and fifth harmonic elimination is proposed to relax the requirements of the filter and to reduce the control complexity of the SMPA for all-digital transmitters. By controlling the pulse width and the center position of three-level sub-pulses, third and fifth harmonic elimination is achieved. Meanwhile, the control complexity of the SMPA is reduced by the decrease in the output-signal-level number. Finally, the feasibility of the method is verified by simulation. For the 16QAM signal with a carrier frequency of 200 MHz, the proposed method can achieve third harmonic suppression of −46.24 dBc and fifth harmonic suppression of −54.05 dBc when coding efficiency reaches 77.51%.