In this work, we present the possibility of producing multiscale hierarchical micro/nanostructures by the femtosecond laser ablation of transition metals (i.e., Ta and W) in water and investigate their polarization-dependent reflectance. The hierarchical micro/nanostructures are composed of microscale-grooved, mountain-like and pit-rich structures decorated with hybrid laser-induced periodic surface structures (LIPSSs). The hybrid LIPSSs consist of low/high and ultrahigh spatial frequency LIPSSs (LSFLs/HSFLs and UHSFLs). LSFLs/HSFLs of 400–600 nm in a period are typically oriented perpendicular to the direction of the laser polarization, while UHSFLs (widths: 10–20 nm and periods: 30–50 nm) are oriented perpendicular to the curvatures of LSFLs/HSFLs. On the microstructures with height gradients, the orientations of LSFLs/HSFLs are misaligned by 18°. On the ablated W metasurface, two kinds of UHSFLs are observed. UHSFLs become parallel nanowires in the deep troughs of LSFLs/HSFLs but result in being very chaotic in shallow LSFLs, turning into polygonal nanonetworks. In contrast, chaotic USFLs are not found on the ablated Ta metasurfaces. With the help of Fourier transform infrared spectroscopy, it is found that microgrooves show an obvious polarization-dependent reflectance at wavelengths of 15 and 17.5 μm associated with the direction of the groove, and the integration of microstructures with LSFs/HSFLs/UHSFLs is thus beneficial for enhancing the light absorbance and light trapping in the near-to-mid-infrared (NIR-MIR) range.