The ablation of lithium niobate (LiNbO3), POLY(tetrafluoroethylene) (PTFE, teflon), poly(methylmethacrylate) (PMMA) and polyimide (PI) by 500 fs UV excimer laser pulses at 248 nm is reported. Time-resolved measurements were carried out with pulse pairs of variable delay in the range from -200 to +200 ps. The ablation rate is very sensitive to the time delay between the two pulses, and -depending on the material and fluence-can increase or decrease for very short time delays. For LiNbO3, efficient shielding is observed within a few picoseconds. For PTFE and PMMA, and the total fluence just above threshold, the ablation rate versus time delay shows an autocorrelation type behavior with a full width at half-maximum below 400 fs, since two-photon absorption dominates the ablation process. For polyimide, excited state absorption is found to decrease the ablation rate for delay times below 30 ps.