The need to improve bioethanol yield from elephant grass has made the optimization of the pretreatment process inevitable. This work studied and determined the optimal alkaline concentration for the pretreatment of elephant grass with sodium hydroxide (NaOH) and hot water under the specified conditions. The pretreatment was performed at different concentrations of sodium hydroxide for a period of 1:30 hr. at 97.5oC. Scanning Electron Microscope (SEM) and Fourier Transform Infrared Spectroscopy (FTIR) were used to determine the effects of the pretreatment on the morphology and structure of the elephant grass. The grass hydrolysate was subjected to simultaneous saccharification and fermentation using cellulase enzyme and bakers’ yeast. Optimum pretreatment condition was obtained by using 0.25 M NaOH, which yielded 6.778g/L reducing sugar. Bioethanol yield was found to be 8.84% of the available sugar. The SEM and FTIR analysis showed that NaOH pretreatment under the determined optimum conditions successfully disintegrated the recalcitrant structure of elephant grass. Hence, NaOH pretreatment at the concentration of 0.25 M exposed to hot water for 1:30 hr. at 97.5oC is a promising condition for bioethanol production from elephant grass.