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Styrene is an important industrial chemical. Although several studies have reported microbial styrene production, the amount of styrene produced in batch cultures can be increased. In this study, styrene was produced using genetically engineered <i>Escherichia coli</i>. First, we evaluated five types of phenylalanine ammonia lyases (PALs) from <i>Arabidopsis thaliana</i> (AtPAL) and <i>Brachypodium distachyon</i> (BdPAL) for their ability to produce <i>trans</i>-cinnamic acid (Cin), a styrene precursor. AtPAL2-expressing <i>E. coli</i> produced approximately 700 mg/L of Cin and we found that BdPALs could convert Cin into styrene. To assess styrene production, we constructed an <i>E. coli</i> strain that co-expressed AtPAL2 and ferulic acid decarboxylase from <i>Saccharomyces cerevisiae</i>. After a biphasic culture with oleyl alcohol, styrene production and yield from glucose were 3.1 g/L and 26.7% (mol/mol), respectively, which, to the best of our knowledge, are the highest values obtained in batch cultivation. Thus, this strain can be applied to the large–scale industrial production of styrene.