We assess the color appearance of the samples with different inks on glossy substrates, five kinds of paper with different gloss levels. The color samples are measured using spectrophotometers under different illuminating/viewing geometries and visually estimated using the psychophysical method of magnitude estimation. The results of the two approaches are compared through the color appearance model of CIECAM02. The experimental data analysis indicates that the 0/45 and 15/0 geometries can be used to describe the two major aspects of gloss effect, the enlargement of color gamut, and the reduction of lightness. The agreement for hue attribute between instrumental measurement and visual assessment is better than those for colorfulness and lightness.