Methane from environmentally friendly anaerobic digestion may be an alternative non-renewable source that is depleting. One of the substrates for that process may be lignocellulose-based materials. The article concerns comparing the environmental impact as well as technical and energy indicators of alternative ways of producing methane from the anaerobic digestion of Pennisetum hybrid. Five scenarios were analyzed: methane production from the anaerobic digestion of the raw grass, the grass subjected to alkaline pretreatment (with 2% NaOH solution at two temperatures), and the grass subjected to mechanical pretreatment (ground to obtain particle sizes <0.18 mm and 0.25–0.38 mm). Multi-criteria decision (MCA) analysis was carried out with the use of five indicators, including life cycle assessment results as well as methane production parameters, in order to optimize this sustainable way of bioenergy production. The purpose of this study was to identify the most cost-effective and environmentally friendly method of Pennisetum hybrid pretreatment in order to optimize the methane production process in terms of environmental, technical, and economic aspects. According to the obtained results, it was stated that the most advantageous solution for the majority of the analyzed indicators turned out to be the mechanical pretreatment with grinding the lignocellulosic biomass into a particle size <0.18 mm.