Herein, we have probed a wide band gap material, CaGa2O4 co-doped with Eu3+/Na+, which is fairly transparent (≥95%) in visible region and efficiently absorbs solar blind UV radiation. Importantly, the absorbed UV energy can be realized both in terms of fluorescence and photoconductivity as well. X-ray diffraction studies confirms that, CaGa2O4 exhibits two orthorhombic polymorphs CaO.Ga2O3 I (major) and CaO.Ga2O3 ΙΙ (minor). Vibrational spectroscopy establishes the first quantitative insight into the phonon frequency of the material. Host itself gives UV-blue and red emission driven by host: band to band and trap level transitions, respectively, under UV excitation. A substantial overlap between emission spectrum of the host and excitation spectrum of Eu3+; decrease in emission intensity and decay time (8.82 μs from 9.2 μs) of the host emission, after Eu3+ doping; and evolution of a short rise-time (~10 μs) in decay curve of Eu3+ reveal that, the host efficiently transfers its energy to Eu3+ ion. Co-doping of Na+ further enhances the emission intensity (~7 times), decay time and rise-time of Eu3+ emission. Likewise the intrinsic behavior of Ga2O3, this material also shows significant transient photoconductivity under UV illumination, photocurrent is of the order of μA, but with slow time constant ~40 min. Thus, excellent optical properties prove superiority over photoconductivity for UV-to-visible converter application. Such WBG optical materials can be coupled to silicon-based commercial detectors for their wide use in areas ranging from invisible flame sensing to UV astronomy, etc.