Herein, nanoporous silica monoliths are used as a morphological template for liquid‐phase synthesis of luminescent carbon nanodots. Two kinds of sol–gel‐derived porous silica samples with the average nanopore sizes of 40 and 7 nm are infiltrated with sucrose/dimethyl sulfoxide solution followed by thermolysis at 170–180 °C. Thermal treatment causes the formation of carbon moieties that are, afterward, extracted into water. The obtained aqueous solutions of carbon dots show intense photoluminescence. The observed emission and excitation bands are strongly affected by the morphology of nanoporous silica template. Larger pore size of silica nanotemplate results in the red shift of the emission and excitation bands.