The Great Observatories All-Sky LIRG Survey (GOALS) is a comprehensive, multiwavelength study of luminous infrared galaxies (LIRGs) in the local universe. Here we present low resolution Spitzer Infrared Spectrograph spectra covering 5-38 μm and provide a basic analysis of the mid-IR spectral properties observed for nearby LIRGs. In a companion paper, we discuss detailed fits to the spectra and compare the LIRGs to other classes of galaxies. The GOALS sample of 244 nuclei in 180 luminous (10 11 L IR /L < 10 12 ) and 22 ultraluminous (L IR /L 10 12 ) IR galaxies represents a complete subset of the IRAS Revised Bright Galaxy Sample and covers a range of merger stages, morphologies, and spectral types. The majority (>60%) of the GOALS LIRGs have high 6.2 μm polycyclic aromatic hydrocarbon (PAH) equivalent widths (EQW 6.2 μm > 0.4 μm) and low levels of silicate absorption (s 9.7 μm > −1.0). There is a general trend among the U/LIRGs for both silicate depth and mid-infrared (MIR) slope to increase with increasing L IR . U/LIRGs in the late to final stages of a merger also have, on average, steeper MIR slopes and higher levels of dust obscuration. Together, these trends suggest that as gas and dust is funneled toward the center of a coalescing merger, the nuclei become more compact and more obscured. As a result, the dust temperature increases also leading to a steeper MIR slope. The sources that depart from these correlations have very low PAH equivalent width (EQW 6.2 μm < 0.1 μm) consistent with their emission being dominated by an active galactic nucleus (AGN) in the MIR. These extremely low PAH EQW sources separate into two distinct types: relatively unobscured sources with a very hot dust component (and thus very shallow MIR slopes) and heavily dust obscured nuclei with a steep temperature gradient. The most heavily dust obscured sources are also the most compact in their MIR emission, suggesting that the obscuring (cool) dust is associated with the outer regions of the starburst and not simply a measure of the dust along the line of sight through a large, dusty disk. A marked decline is seen for the fraction of high EQW (star formation dominated) sources as the merger progresses. The decline is accompanied by an increase in the fraction of composite sources while the fraction of sources where an AGN dominates the MIR emission remains low. When compared to the MIR spectra of submillimeter galaxies (SMGs) at z ∼ 2, both the average GOALS LIRG and ULIRG spectra are more absorbed at 9.7 μm and the average GOALS LIRG has more PAH emission. However, when the AGN contributions to both the local GOALS LIRGs and the high-z SMGs are removed, the average local starbursting LIRG closely resembles the starburst-dominated SMGs.