Mid-infrared (MIR) wavelengths (2–10 μμm) open up a new paradigm for femtosecond laser–solid interactions. On a fundamental level, compared to the ubiquitous near-IR (NIR) or visible (VIS) laser interactions, MIR photon energies render semiconductors to behave like high bandgap materials, while driving conduction band electrons harder due to the λ2 scaling of the ponderomotive energy. From an applications perspective, many VIS/NIR opaque materials are transparent for MIR. This allows sub-surface modifications for waveguide writing while simultaneously extending interactions to higher order processes. Here, we present the formation of an extreme sub-wavelength structure formation (∼λ/100) on a single crystal silicon surface by a 3600 nm MIR femtosecond laser with a pulse duration of 200 fs. The 50–100 nm linear structures were aligned parallel to the laser polarization direction with a quasi-periodicity of 700 nm. The dependence of the structure on the native oxide, laser pulse number, and polarization were studied. The properties of the structures were studied using scanning electron microscopy (SEM), atomic force microscopy (AFM), cross-sectional transmission electron-microscopy (CS-TEM), electron diffraction (ED), and energy-dispersive X-ray spectroscopy (EDX). As traditional models for the formation of laser induced periodic surface structure do not explain this structure formation, new theoretical efforts are needed.