Carbon quantum dots (C-QDs) with different size distributions and surface characteristics can exhibit good emission properties in the visible and near-infrared (NIR) regions, which can be applicable in optoelectronic devices as well as biomedical applications. Optical properties of colloidal C-QDs in distilled water at different concentrations produced using a method of alkali-assisted surfactant-free oxidation of cellulose acetate is presented. The structural and optical properties of colloidal C-QDs at different concentrations were investigated, with the aim of clarifying the main mechanisms of photoluminescence emissions. We observed a wide range of tunable visible to NIR emissions with good stability from the C-QD colloids at different applied excitation wavelengths. The colloids show dual emissions with maxima at and 775 nm (blue and NIR emissions) when excited at the wavelength range near the energy gaps of the C-QDs. Moreover, by increasing the excitation wavelength, tunable visible emissions at the spectral range of 475 to 550 nm are observed. A detailed analysis of the results shows that the blue and NIR luminescence of colloidal C-QDs originate from the oxide-related surface effects whereas quantum confinement is the responsible mechanism for tunable visible emissions of the C-QD colloid.