Plumbum (Pb)-based lanthanum doped zirconate titante piezoelectric ceramic (PZT), silicon (Si) and polydimethylsiloxane (PDMS) are fabricated with 248 nm KrF excimer laser. The processing effects of excimer laser on the above three materials are investigated. To solve the problem that the PZT diaphragm fabricated with traditional dicing process is fragile, the processing performance of PZT microstructure with excimer laser is investigated. The processing parameters and the relationship among processing parameters, processing depth and processing width of PZT substrate are obtained when we adjust several parameters of excimer laser, such as laser pulse energy, pulse frequency, scanning speed and scanning times. Effects of auxiliary gas on the PZT surface roughness processed with excimer laser are studied. The PZT-Si cantilever and PZT-Si diaphragm are fabricated with excimer laser, and their piezoelectric properties are tested. Results show that the two PZT micro-piezoelectric structures fabricated by excimer laser have excellent piezoelectric performance, and the structures can be used as key devices of micro-piezoelectric actuator. The feasibility of processing PZT microstructure with excimer laser is proved.