In order to investigate the photoelectric characteristics of 80 × 120 µm2 mini-light-emitting-diodes (mini-LEDs) with sidewall passivation by atomic layer deposition (ALD), this paper uses the techniques of spectrometer-based spectroradiometer and microscopic hyperspectral imaging (µ-HSI). The temperature-dependent electroluminescence is measured using a spectrometer-based spectroradiometer. By analyzing the rising parts of external quantum efficiency at room temperature with a two-level model, the difference of physical mechanisms between mini-LEDs with ALD and without ALD are determined. In addition, the thermal quenching indicates that the ALD sidewall passivation can enhance the temperature stability of the mini-LEDs. The ALD sidewall passivation also enhances the light extraction efficiency according to the theoretical calculation of transmittance. Moreover, the µ-HSI technique is used to evaluate different local areas of mini-LEDs. The obtained results reveal the optimization on lateral distribution of current density within the chip after sidewall passivation.