Thermodynamic feasibility of solvolysis of benzylamine by ethanol has been examined theoretically. Calculation shows that solvolysis of benzylamine by ethanol to produce benzylethylether should not be possible thermodynamically, but solvolysis of N-ethylbenzylamine may be possible at high temperatures. This theoretical prediction has been substantiated by carrying out experiments on solvolysis of benzylamine by ethanol under different reaction conditions. Under optimum reaction condition 53 mol% of benzylethylether can be obtained at 507 K under reaction pressure of about 9.4 MPa. Solvolysis of benzylamine by ethanol occurs via intermediate formation of N-ethylbenzylamine. A reaction mechanism has been suggested.