The aim was to evaluate the translucency, opalescence, and fluorescence of highly translucent zirconia, lithium disilicate, and bovine teeth. One mm-thick specimens of five monolithic zirconia systems, two glass-ceramics, and bovine enamel/dentin were investigated. A spectrophotometer (Ci7600) was used to measure the CIELab color coordinates, and the translucency and opalescence values were obtained. For evaluating the fluorescence emission, the differences in spectral reflectance by the UV component of illumination were calculated. The microstructures of ceramic specimens were examined with a scanning electron microscope and the chemical compositions were determined with an X-ray fluorescence spectrometer. Mechanical properties were appraised with three-point bending strength, indentation fracture toughness, and Vickers hardness. Data were analyzed using a one-way ANOVA, followed by Tukey’s multiple comparison test (α = 0.05). A higher yttria content (5 mol%) significantly improved the translucency of zirconia ceramics, while they were less translucent than lithium disilicate (p < 0.05). Lowering the alumina content below 0.05 wt.% enhanced the translucency (p < 0.05), but a small amount of alumina was still required to obtain full densification. 0.05 wt.% Fe was used to increase the chroma of zirconia specimens without compromising their mechanical properties. The Er-containing zirconia specimen showed a maximal fluorescence emission at 430 nm. The degree of opalescence was affected by the microstructures of ceramic materials. The microstructure, incorporation of a secondary phase, and sintering behavior can have a strong impact on the final mechanical and optical properties of dental ceramics. Addition of small amounts of metal oxides can affect the translucency, opalescence or fluorescence qualities of zirconia