A combination of time-resolved shadowgraphy and laser-induced breakdown spectra (LIBS) was performed to investigate the ablation behavior of United States Geological Survey (USGS) and National Institute of Standards and Technology (NIST) geological standard samples when ablated by focused nanosecond laser pulses in air. The shock wave (SW) radius achieved 1535 μm at 743 ns for the BCR-2G, and 1513 μm at 759 ns for the NIST SRM 612 standard samples when a laser pulse energy of 17 mJ was used. The maximum speed, pressure, temperature, and density of the shock wave were 5435 m/s, more than 600 MPa, 3 × 105 K, and 7.76 kg/m3, respectively, for NIST SRM 612. Three SWs were generated as these standard samples were ablated. Laser-induced SWs are expected to contribute to attain an approximate matrix-matched reference material, which would render direct solid concentration analysis possible.