One approach to improving the output power of ultraviolet (UV-C) light-emitting diodes (LEDs) is to adopt an electron-blocking layer (EBL) with a high barrier. However, the intended effect may not be realized because of the composition pulling effect, which is the unintended occurrence of a gradient layer at an AlGaN/AlGaN hetero-interface with substantial differences in the Al composition. Here, we demonstrate that low-temperature growth (i.e., <1000 °C) can be used to control the unintentional gradient layer at an AlN/AlGaN hetero-interface between a barrier layer and AlN-EBL with a difference in Al compositions of more than 30%. LEDs with an emission wavelength of 265 nm were fabricated, and an AlN-EBL was grown at low temperature to realize an abrupt interface. At an applied current of 100 mA, growing the EBL under low-temperature conditions improved the forward voltage by 0.5 V and remarkably improved the peak luminous intensity by 1.4–1.6 times. Our results can be used to realize UV-C LEDs with a steep EBL and further improve their device characteristics.