The patterning of polydimethylsiloxane (PDMS) into complex two-dimensional (2D) or 3D shapes is a crucial step for diverse applications based on soft lithography. Nevertheless, mould replication that incorporates time-consuming and costly photolithography processes still remains the dominant technology in the field. Here we developed monolithic quasi-3D digital patterning of PDMS using laser pyrolysis. In contrast with conventional burning or laser ablation of transparent PDMS, which yields poor surface properties, our successive laser pyrolysis technique converts PDMS into easily removable silicon carbide via consecutive photothermal pyrolysis guided by a continuous-wave laser. We obtained high-quality 2D or 3D PDMS structures with complex patterning starting from a PDMS monolith in a remarkably low prototyping time (less than one hour). Moreover, we developed distinct microfluidic devices with elaborated channel architectures and a customizable organ-on-a-chip device using this approach, which showcases the potential of the successive laser pyrolysis technique for the fabrication of devices for several technological applications.