We report the synthesis, characterization, and photophysical properties of a series of organic receptors and their corresponding Re-I and Ru-II metal complexes as anion probes featuring bis(sulfonamide) interacting sites incorporating highly chromophoric pi-conjugated quinoxaline moieties. The interactions with various anions were extensively investigated. These probe molecules are capable of recognizing F-, OAc-, CN-, and H2PO4- with different sensitivities. The probe-anion interactions can be easily visualized via naked-eye colorimetric or luminescent responses. Probe 1 has the weakest acidic sulfonamide N-H protons and therefore simply forms hydrogen-bonding complexes with F-, OAc-, CN-, and H2PO4-. Probe 2 undergoes a stepwise process with the addition of F- and OAc-: formation of a hydrogen-bound complex followed by sulfonamide N-H deprotonation. Direct sulfonamide N-H deprotonation occurs upon the addition of CN-, while only a hydrogen-bound complex forms with the H2PO4- ion for probe 2 in a dimethyl sulfoxide (DMSO) solution. Similar probe-anion interactions occur in probe 3 with the addition of F-, CN-, or H2PO4-. However, only a genuine hydrogen-bound complex forms in the presence of the OAc- ion in a DMSO solution of probe 3 because of the subtle difference in the pKa values of sulfonamicle N-H protons when probes 2 and 3 are compared. Coordination of probe 1 to a Re-1 center or probe 2 to a Ru-II center increases the intrinsic acidity of sulfonamide N-H protons and results in an enhanced sensitivity to anions.