Mo-based transition metal dichalcogenide (TMD) materials are being widely researched as a catalyst for hydrogen evolution reaction (HER) due to their near-zero hydrogen adsorption energy and high density of active reaction sides. Only the edges of the MoS2 layer have high catalytic performance, leading to the need for nanostructured MoS2. Multiwalled carbon nanotubes (MWCNTs), which have great electrical conductivity and mechanical and chemical stability, are a suitable framework for nanoscale MoS2 deposition. In this work, we fabricated a free-standing MWCNT paper through repeatedly electrophoretic deposition of MWCNTs-COOH onto indium tin oxide coated polyethylene terephthalate (ITO-PET), with a decoration of shell@core structured MoSx@MoOy (2 < x < 3 and 2 < y < 3) nanoparticles through potentiostatic technique, followed by a substrate removal in a neutral medium. The thickness of the MWCNT film increases by approximately 5 µm with each deposition step and shows good electrical conductivity. The XRD pattern shows the hexagonal and orthorhombic structure of MoSx and MoOy respectively. Raman spectra and XRD patterns confirm the formation of amorphous MoSx and MoOy onto the outer wall of MWCNTs, increase the size of the nanotubes, as well as enhance the mechanical stability of the as prepared thin film.