The demand for enhanced optical properties in advanced fluorescence technologies has driven research into the structure-property relationship of fluorophores. In this paper, we use naphthalene fluorophores NaDC-Aze and PhDO-Aze as a case study to emphasize the pivotal role of cross conjugation in tuning the optical structure-property relationship. NaDC-Aze and PhDO-Aze, formed by hybridizing two distinct conjugated systems in a single naphthalene molecule, exhibit spectral characteristics from both conjugated systems. Experimental data and theoretical calculations demonstrate the coexistence of two electron-delocalization systems in a cross-conjugation manner in both NaDC-Aze and PhDO-Aze. The cross-conjugation fluorophores exhibit high brightness, large Stokes shift, and a broad absorption wavelength range by combining distinct spectral properties from its parent fluorophores. These spectral properties will be advantageous for certain applications (i.e., panchromatic absorption in organic solar cells, and fluorophores compatible with a wide range of excitation wavelengths).