This study reports the near-UV to blue photoluminescence (PL) from solution-processed graphene oxide (GO). The PL characteristics and their dependence on GO reduction indicate that the emission originates from the recombination of electron-hole (e-h) pairs localized within small $sp^2$ carbon clusters embedded in an $sp^3$ matrix. The results suggest that GO provides a parent structure on which fluorescent components can be chemically engineered without losing macroscopic structural integrity, offering a unique route for solution-processable optoelectronics devices. The study also explores the electrical transport properties of GO, showing that the PL intensity increases initially with reduction due to the formation of additional small $sp^2$ domains, but decreases after extensive reduction due to percolation among these domains, facilitating non-radiative recombination. The findings highlight the potential for engineering desired $sp^2$ structures in graphene to achieve highly efficient and tunable PL for optoelectronic applications.This study reports the near-UV to blue photoluminescence (PL) from solution-processed graphene oxide (GO). The PL characteristics and their dependence on GO reduction indicate that the emission originates from the recombination of electron-hole (e-h) pairs localized within small $sp^2$ carbon clusters embedded in an $sp^3$ matrix. The results suggest that GO provides a parent structure on which fluorescent components can be chemically engineered without losing macroscopic structural integrity, offering a unique route for solution-processable optoelectronics devices. The study also explores the electrical transport properties of GO, showing that the PL intensity increases initially with reduction due to the formation of additional small $sp^2$ domains, but decreases after extensive reduction due to percolation among these domains, facilitating non-radiative recombination. The findings highlight the potential for engineering desired $sp^2$ structures in graphene to achieve highly efficient and tunable PL for optoelectronic applications.