New V-shaped xanthene dyes 3–6 containing piperidino groups at the resonance sites on their skeletons were constructed as second-generation V-shaped dyes and their functions were investigated. The non-symmetric compound 5 had higher solubility and gave a higher fluorescence quantum yield and longer emission wavelength compared with those of previously reported V-shaped xanthene dyes with hydroxyl groups 1 and 2. Furthermore, compound 5 stained living cells, enabling bright fluorescence imaging.