ObjectiveThe aim of this in vitro study is to evaluate the masking ability of polymer‐infiltrated ceramic‐network materials (PICN) with different translucencies and thicknesses on multiple types of substrates.Materials and MethodsCeramic samples were prepared of VITA ENAMIC blocks in two different translucencies (2M2‐T, 2M2‐HT) in a thickness range of 0.5–2.5 mm (±0.05 mm). Layered specimens were obtained using composite substrates in nine shades and transparent try‐in paste. Spectral reflectance of specimens was measured using a Konica Minolta CM‐3720d spectrophotometer and D65 standard illumination. CIEDE2000 color difference (ΔE00) between two samples was evaluated using 50%:50% perceptibility and acceptability thresholds. Specular component of the reflection was examined with Specular Component Excluded (SCE) and Included (SCI) settings. Statistical evaluation was performed by linear regression analysis, Kruskal–Wallis test, and multiplicative effect analysis.ResultsAn increase in thickness of 0.5 mm reduces ΔE00 of HT samples to 73.5%, of T samples to 60.5% (p < 0.0001). Five substrates with HT specimens, and three substrates with T specimens had significantly different results from average (p < 0.05). There is a significant difference between SCE and SCI data depending on the wavelength (p < 0.0001).ConclusionsMasking ability of PICN materials is influenced by the thickness and translucency of the ceramic, and by the substrate. Reflection of the examined PICN material is characterized by both diffuse and specular reflection.Clinical SignificanceAlthough PICN materials have been available on the market for 10 years now, there is a lack of information regarding their masking ability. Acquiring in‐depth data and thereby practical experience of the factors affecting the esthetics of PICN materials is essential for creating perfectly lifelike restorations.