Range sidelobe is a common and widely concerned issue in synthetic aperture radar (SAR) imaging. The sidelobe of strong scatters could cover weak targets and reduce the quality of SAR images, increasing the difficulty in interpretation. Due to the principle of energy conservation, reducing the sidelobe will reduce the range resolution of SAR for the single waveform design. By taking full advantage of the degrees of freedom of the transmitter, transmitting multiple waveforms, and exploiting the information discrepancy between pulses, we can overcome this limitation. Complementary sequences are a typical example since the range sidelobe of the sequences can be theoretically summed up to zero. Due to the transmission of different waveforms between pulses, an amplitude-phase modulation will be introduced in the azimuth dimension of SAR echo, which, in turn, leads to the Doppler spectrum aliasing and unexpected energy spikes outside the main energy region of SAR point spread function (PSF). Seeking to suppress the range sidelobe and meanwhile mitigate the spikes caused by waveform agility in SAR, we first establish the expression of the echo under the agile transmitting mode. Then, we propose an SAR PSF shaping (SAR-PSFS) method to suppress the integrated sidelobe level (ISL) of the whole range sidelobe plane in the SAR image via complementary waveform optimization. The inexact alternating direction penalty method (IADPM) framework is adopted to solve the resulting nonconvex optimization problem. Simulation results show that the proposed method outperforms the nonlinear frequency-modulation (NLFM) signal with a 5.46-dB lower integrated sidelobe ratio (ISLR) under the same mainlobe width. Besides, the range sidelobe can be effectively canceled with a 3.26-dB lower peak sidelobe ratio (PSLR) and a 4.99-dB lower ISLR compared with the Hanning window while maintaining the range resolution with the spikes caused by waveform agility effectively mitigated.