Conversion of Pennisetum purpureum × Pennisetum americanum (Napier Pak Chong1) press cake into biobutanol using Clostridium beijerinckii TISTR 1461 was proposed as an alternative to combustion in this study. The optimum conditions for biobutanol fermentation were determined using a full factorial design and a central composite design of experiment. The studied factors were initial pHs (5.50–6.50) and sugar concentrations (40–60 g/L), while butanol yield (g/g reducing sugar utilized) was specified as the optimization response. The results showed that the suitable enzyme loading of alkali-pretreated press cake (at 3% w/w NaOH, 10% substrate loading, boiling at 90 °C, with a reaction time of 1 h) was 10 FPU/g biomass, which provided a glucose yield of 345 mg/g pretreated press cake. The optimized pH and reducing sugar concentration were 6.08 and 43 g/L, respectively. At these conditions, the maximum butanol yield from the hydrolysate of NaOH-pretreated press cake was 0.135 g/g reducing sugar utilized (0.30 g/g glucose utilized). Apart from the possibility of generating much less pollution, it was estimated that using the same amount of press cake, butanol production could possibly have a value comparable to that obtained from combustion for electricity production. A new concept for overall Napier Pak Chong1 grass utilization was also presented.