Laser-induced graphene (LIG) is a graphenic material synthesized from a polymeric substrate through point-by-point laser pyrolysis. It is a fast and cost-effective technique, and it is ideal for flexible electronics and energy storage devices, such as supercapacitors. However, the miniaturization of the thicknesses of the devices, which is important for these applications, has still not been fully explored. Therefore, this work presents an optimized set of laser conditions to fabricate high-quality LIG microsupercapacitors (MSC) from 60 µm thick polyimide substrates. This is achieved by correlating their structural morphology, material quality, and electrochemical performance. The fabricated devices show a high capacitance of 22.2 mF/cm2 at 0.05 mA/cm2, as well as energy and power densities comparable to those of similar devices that are hybridized with pseudocapacitive elements. The performed structural characterization confirms that the LIG material is composed of high-quality multilayer graphene nanoflakes with good structural continuity and an optimal porosity.