Context. A large fraction of early-type galaxies (ETGs) shows emission lines in their optical spectra, mostly with LINER characteristics. Despite the number of studies, the nature of the ionization mechanisms is still debated. Many ETGs also show several signs of rejuvenation episodes. Aims. We aim to investigate the ionization mechanisms and the physical processes of a sample of ETGs using mid-infrared spectra. Methods. We present here low resolution Spitzer-IRS spectra of 40 ETGs, 18 of which from our proposed Cycle 3 observations, selected from a sample of 65 ETGs showing emission lines in their optical spectra. We homogeneously extract the mid-infrared (MIR) spectra, and after the proper subtraction of a "passive" ETG template, we derive the intensity of the ionic and molecular lines and of the polycyclic aromatic hydrocarbon (PAH) emission features. We use MIR diagnostic diagrams to investigate the powering mechanisms of the ionized gas. Results. The mid-infrared spectra of early-type galaxies show a variety of spectral characteristics. We empirically sub-divide the sample into five classes of spectra with common characteristics. Class-0, accounting for 20% of the sample, are purely passive ETGs with neither emission lines nor PAH features. Class-1 show emission lines but no PAH features, and account for 17.5% of the sample. Class-2, in which 50% of the ETGs are found, as well as having emission lines, show PAH features with unusual ratios, e.g. 7.7 μm/11.3 μm ≤ 2.3. Class-3 objects (7.5% of the sample) have emission lines and PAH features with ratios typical of star-forming galaxies. Class-4, containing only 5% of the ETGs, is dominated by a hot dust continuum. .82 μm, is used to investigate the different mechanisms ionizing the gas. According to the above diagram most of our ETGs contain gas ionized via either AGN-like or shock phenomena, or both. Conclusions. Most of the spectra in the present sample are classified as LINERs in the optical window. The proposed MIR spectral classes show unambiguously the manifold of the physical processes and ionization mechanisms, from star formation, low level AGN activity, to shocks (H 2 ), present in LINER nuclei.