Carbon nanodots (CNDs) have many fascinating properties, such as optical properties (UV-Visible absorption and fluorescence emission), which make them good candidates in many applications, such as photocatalysts for the degradation of several organic pollutants. This study aims to synthesize CNDs from olive solid wastes at different carbonization temperatures from 300 to 900 °C and study the effect on the optical properties of the CNDs, such UV-Vis, fluorescence, quantum yield, and energy bandgap, in addition to the influence on the photoactivity of the CNDs as photocatalysts for the degradation of methylene blue (MB). CNDs were prepared from olive solid wastes (OSWs) by pyrolysis at different temperatures (300–900 °C) for conversion to carbonized material, and then oxidized chemically in the presence of hydrogen peroxide (H2O2). It was found that an increase in the carbonization temperature of the OSWs leads to an increase in the product yield with a maximum value at 500 °C, and it then decreased dramatically. On the other hand, a decrease in fluorescence due to the diminishment of oxygen groups and the destruction of the surface of the CNDs was observed. The higher quantum yield (5.17%) and bandgap (2.77 eV) were achieved for CNDs prepared from OSWs that carbonized at 300 °C. The rate and degradation efficiency of MB were studied with the different synthesized CNDs, and it was found that an increase in the carbonization temperature leads to a decrease in the rate and degradation efficiency of MB, with the highest degradation rate of 0.0575 min−1 and degradation efficiency of 100% after 120 minutes of light irradiation being realized for the sample carbonized at 300 °C.