Structural and optical properties of double sodium–bismuth molybdate NaBi(MoO4)2 semiconductor compound was investigated by X-ray diffraction, Raman and transmission experiments. From the X-ray diffraction experiments, the crystal that has tetragonal structure was obtained. Vibrational modes of the crystal were found from the Raman experiments. Transmission experiments were performed in the temperature range of 10-300 K. Derivative spectroscopy analysis and absorption spectrum analysis were performed to get information about the change in band gap energy of the crystal with temperature. It was observed that the band gap energies of the crystal at different temperatures obtained from these techniques are well consisted with each other. By the help of absorption spectrum which was obtained from transmission measurements performed at varying temperatures, absolute zero value of the band gap and average phonon energy as 3.03 ± 0.02 eV and 〈E_ph 〉 = 24 ± 0.2 meV, respectively. Moreover, based on absorption spectrum analysis the Urbach energy of the crystal was obtained as 0.10 eV.