Rice straw is among the most abundant herbaceous biomass, and regarded as the central feedstock for bioethanol production in Japan. We found that significant amounts of soft carbohydrates (SCs), defined as carbohydrates readily recoverable by mere extraction from the biomass or brief enzymatic saccharification, exist in rice straw in the form of free glucose, free fructose, sucrose, starch, and β-1,3-1,4-glucan. Based on the finding, we proposed a simple method for bioethanol production from rice straw samples with SCs, by a heat treatment for sterilization and starch gelatinization, followed by simultaneous saccharification/fermentation with Saccharomyces cerevisiae. This method would offer an efficient process for bioethanol production without the aid of harsh thermo/chemical pretreatment step.