Ionization-assisted spectral broadening of high-energy 10.6 μm laser pulses in a gas-filled hollow waveguide is shown to yield single-cycle pulses with multiterawatt peak powers in the mid-IR. While the highest quality of pulse compression is achieved in the regime of weak ionization, careful management of complex ionization-assisted spectral broadening of guided-wave fields is the key to compressing the output of advanced high-power mid-IR laser sources to single-cycle pulse widths.