Genuine leather is produced from animal skin by chemical tanning using chemical or vegetable agents, while synthetic leather is a combination of fabric and polymer. The replacement of natural leather by synthetic leather is becoming more difficult to identify. In this work, Laser Induced Breakdown Spectroscopy (LIBS) is evaluated to separate between very similar materials: leather, synthetic leather, and polymers. LIBS is now widely employed to provide a specific fingerprint from the different materials. Animal leathers processed with vegetable, chromium, or titanium tanning were analyzed together with polymers and synthetic leather from different origins. The spectra exhibited typical signatures from the tanning agents (Cr, Ti, Al) and the dyes and pigments, but also from polymer characteristic bands. The principal factor analysis allowed to discriminate between four main groups of samples representing the tanning processes and the polymer or synthetic leather character.