The brewing industry generates, as the primary coproduct, brewers’ spent grain (BSG). In Mexicali, Baja California, Mexico, there are 17 companies that generated 282 tons of BSG by 2016. Cattle feeding is the most common type of disposal for this waste. However, it can be valorized for the production of bioenergy or as a source of added-value products. Therefore, the objective of the present work was to assess the physicochemical properties of the brewers’ spent grain from a local craft brewery, to choose the most appropriate exploitation route. Chemical and morphological analyses were carried out by energy dispersive X-ray fluorescence spectroscopy (EDX), scanning electron microscopy, and the higher heating value determination. The results of the proximate analyses were 72.32% moisture, 78.47% volatile matter, 17.48% fixed carbon, and 4.05% ash. The results of the chemical analysis for extractables were 5.23% using organic solvent and 50.25% using hot water. The content determination were 17.13% lignin, 26.80% cellulose, and 37.17% hemicellulose. The results of the ultimate analysis were 43.59% C, 6.18% H, 3.46% N, and 37.22% O. The higher heating value experimentally obtained was 18.70 MJ/kg. Moreover, in the EDX analysis, Ca, P, K, and S were mainly found. It is recommendable to valorize the BSG through the xylitol, bioethanol or biogas production, because of its high moisture, hemicellulose and cellulose content.