This study investigates the interaction of picosecond laser pulses with sapphire and brass in air using scanning electron microscopy. A picosecond laser system operating at a wavelength of 785 nm, pulse width of 110 ps, and variable repetition rate (1–1000 Hz) was used in this study. The pulse width applied in this work was not widely investigated as it lies in the gap between ultrashort (femtosecond) and long (nanosecond) pulse width lasers. Different surface morphologies were identified using secondary electron and backscattered electron imaging of the ablated material. Thermal ablation effects were more dominant in brass than in sapphire. Exfoliation and fractures of sapphire were observed at high laser fluence. Compared with brass, multiple laser pulses were necessary to initiate ablation in sapphire due to its poor absorption to the incident laser wavelength. Ablation rate of sapphire was lower than that of brass due to the dissipation of a portion of the laser energy due to heating and fracturing of the surface.