The long-lived radical R6G•, derived from the cationic dye rhodamine 6G (R6G+) by reduction, is of growing interest in photoredox catalysis. This manuscript discusses three methods of its preparation in dimethylsulfoxide, highlighting spectral differences due to solvatochromism, co-solutes, and the basicity of the solution. Upon excitation, R6G•* can release an electron to a substrate molecule or as a solvated electron, leading back to R6G+. However, a second reduction of R6G• is not observed to be reversible here, decreasing the overall concentration of R6G• and R6G+ with time. R6G+ can also be deprotonated to R6G1 under basic conditions, and even double deprotonation to R6G2− is possible, though this may undergo irreversible reaction over time. Excitation of R6G1 leads to the formation of a photoproduct stable for seconds, which then reforms R6G1. If R6G• is exposed to basic conditions in the presence of oxygen, it is oxidized to R6G+, which is then quickly deprotonated to yield R6G1 again. Hence, in basic solution, R6G1 is the predominant species, so that other light-induced reaction pathways than with R6G+ are accessible. It remains to be determined whether the photoproduct of R6G1 could be beneficial for a photocatalytic application under strongly basic conditions.