We designed a femtosecond (fs) + picosecond (ps) double-pulse sequence by using a Mach–Zehnder-like apparatus to split a single 120 fs pulse into two sub-pulses, and one of them was stretched to a width of 2 ps by a four-pass grating system. Through observing the ripples induced on the ZnO surface, we found the ionization rate appeared to be higher for the sequence in which the fs pulse arrived first. The electron rate equation was used to calculate changes of electron density distribution for the sequences with different delay times. We suggest that using a temporally shaped fs+ps pulse sequence can achieve nonlinear ionization control and influence the induced ripples.