The photocatalysis process with high selectivity is a very important research forefront for the semiconductor photocatalytic decomposition of organic pollutants. However, the rational design of efficient photocatalysts with high selectivity is still a challenge. Here, we present an open framework chalcogenide (Heta)(8)[In14Sn2Zn4Se33] (Heta = ethanolamine-H+) (compound 1) constructed from T4 supertetrahedral clusters [In14Sn2Zn4Se35](12-) with visible light-driven selectively photocatalytic degradation activity. Single-crystal XRD analysis shows that compound 1 crystallizes in I4(1)/acd (no. 142) space group, with a = b = 24.3462(2) angstrom, c = 45.0062(9) angstrom, V = 26676.9(7) angstrom(3), and Z = 8. Under visible-light irradiation, the selectively photocatalytic activities of 1 were evaluated by photodegradation of two kinds of cationic dye molecules, i.e., methylene blue (MB) and rhodamine B (RhB), against two anionic dyes, methyl orange (MO) and Kermes red (KR), with different sizes. We show that the adsorption capability and charge-matching between organic dyes and the supertetrahedral cluster together with a suitable band structure make it an excellent and selective photocatalyst. This is the first example of an open-framework chalcogenide based on supertetrahedral T4 for the selectively semiconductor photocatalytic decomposition of organic dyes.