Polylactide nanocomposites with multi-walled carbon nanotubes (PLA/MWCNT) in the form of porous foams made of a biocompatible, biodegradable and environmentally friendly polymer with a small amount of carbon nanotubes, were investigated in this work. Additionally, PLA/MWCNT porous nanocomposites were coated with MWCNTs using the electrophoretic deposition method (EPD). All samples were characterized by a porosity of about 90%, showing pore sizes in the range of 100 to 200 μm, for PLA/MWCNT foam, however, EPD deposition resulted in an decrease in the number of smaller pores in PLA/MWCNT + MWCNT (EPD) foam. The porous polymer (PLA) matrix, shows almost twofold increase in crystallinity while depth penetrating the volume of the sample. The crystallinity, of the PLA/MWCNT foam, at first is growing then it gradually lowers, while for the PLA/MWCNT + MWCNT(EPD) foam almost does not change. This behavior points toward significant distinction between surface and interior of the samples. A detailed analysis of Raman spectra indicates related carbon structures occurring in the nanomaterial foams: graphene and graphite phases, CNT and also carbon amorphous phases. The characteristics of a single-shell vibration are visible by the character of the G-band. The estimated crystallite size in PLA/MWCNT + MWCNT(EPD) is about 3 times smaller than that in the PLA/MWCNT.