Surface groups of carbon nanodots (CNDs) play a key role in modulating their photoluminescence (PL) properties. However, most of the as-prepared CNDs are complex mixtures of CNDs bearing different surface groups. Thus, the purification of CNDs is essential to reveal the PL mechanism of CNDs. Herein, we present a facile method to synthesize hydroxyl (-OH) free CNDs, followed by intelligently guided column chromatographic separation of CNDs with specific functional groups according to their degree of polarity. After systematic investigation of the separated non-polar CNDs (NP-CNDs) and polar CNDs (P-CNDs), it is revealed that radiative photon emission dominates in the NP-CNDs, which exhibits excitation wavelength-independent emissions. In contrast, an increase in the solvent polarity of P-CNDs improves Frank-Condon excited state stabilization to achieve excitation wavelength-dependent emissions. In particular, white-light emitting P-CNDs with CIE coordinates of (0.332, 0.336) are produced. These findings provide new insights into the nature of the PL mechanism for CNDs, which may pave the way towards the rational design of highly efficient and emission tunable CNDs for various applications.