A new synthetic method for the construction of benzoazepine analogues has been developed employing <i>ortho</i>-arylmethylbenzyl azide derivatives as precursors using an azide rearrangement reaction. In this work, 14 benzoazepine compounds were successfully synthesized in moderate to excellent yields. All synthetic benzoazepines were evaluated for their cytotoxicity against normal human kidney cell line (HEK cell). The results showed that compound <b>18c</b> had the lowest cytotoxicity (IC<sub>50</sub> = 65.68 μM) among tested compounds, which was comparable with the antianxiety drug diazepam (IC<sub>50</sub> = 87.90 μM). Based on the cytotoxicity results, five benzoazepine analogues (compounds <b>18c</b>, <b>18h</b>, <b>18j</b>, <b>18n</b>, and <b>18p</b>) were selected to determine the antianxiety effect on stressed rats using elevated plus maze (EPM) and open field test (OFT) methods. Interestingly, compound <b>18c</b> showed better anxiolytic activity than diazepam without a sedative effect by showing superior hyperlocomotor activity. Therefore, this discovery could pave the way for drug development to treat patients with anxiety disorder.