Halogenated tryptanthrin and aminotryptanthrin were synthesized from indigo or isatin precursors. Dibromo- and tetrabromo-tryptanthrin were obtained from indigo dyes following green chemistry procedures, through microwave-assisted synthesis in mild oxidation conditions. Spectral and photophysical properties of the compounds, including quantitative determination of all the different deactivation pathways of S1 and T1, were obtained in different solvents and temperatures. The triplet state (T1) has a dominant role on the photophysical properties of these compounds, which is further enhanced by the halogens at the fused-phenyl rings. Substitution with an amino group, 2-aminotryptanthrin (TRYP-NH2), leads a dominance of the radiative decay channel. Moreover, with the sole exception of TRYP-NH2, S1 ~  ~  > T1 intersystem crossing constitutes the dominant route, with internal conversion playing a minor role in the deactivation of S1 in all the studied derivatives. In agreement with tryptanthrin, emission of the triplet state of tryptanthrin derivatives (with exception of TRYP-NH2), was observed together with an enhancement of the singlet oxygen sensitization quantum yield: from 70% in tryptanthrin to 92% in the iodine derivative. This strongly contrasts with indigo and its derivatives, where singlet oxygen sensitization is found inefficient.