We present a systematic investigation of the photoluminescence (PL) from singlestrand DNA (ssDNA) with different bases (T, A, C and G) and different base numbers (20, 35 and 56). We find that the features of the PL emission from these samples depend sensitively and characteristically on the base structure and base number of the ssDNA.The results obtained from the PL and PL excitation (PLE) measurements indicate that the dependence of the PL and PLE peak wavelengths upon the excitation wavelength can exhibit different features for ssDNA with different base structures and base numbers.Through examining the dependence of the PL and PLE peaks along with the amplitude of the PL peaks upon the excitation wavelength, we are able to identify optically the ssDNA with different bases and the same base but with different base numbers. Thus, one can achieve a non-invasive and label free characterization of the ssDNA by the standard PL measurement. We also propose and examine the possible mechanisms for PL from ssDNA in different excitation wavelength regimes. It is found that the PL from ssDNA is akin to that from a direct band-gap semiconductor with radiative impurity states. This work is relevant to the application of the state-of-the-art optical technique for the characterization and investigation of the DNA structures.