The new complex [Rh
2
(phen)
2
(CH
3
CN)
6
](BF
4
)
4
(
1
) was synthesized and characterized in solution and its crystal structure was determined. Irradiation of
1
with visible light (
λ
irr
>590 nm) in water results in the release of two equatorial CH
3
CN ligands, CH
3
CN
eq
, as well as in the formation of mononuclear radical Rh(II) fragments stemming from the homolytic photocleavage of the metal–metal bond. The photoproducts, identified by electrospray ionization mass spectrometry, include [Rh(phen)(CH
3
CN)(OH)]
+
and [Rh(phen)(CH
3
CN)(H
2
O)
3
(BF
4
)]
+
. The quantum yield for the photochemical transformation of
1
in H
2
O exceeds unity (
Φ
550 nm
=1.38) indicative of dark reactions following the initial photoprocess. DNA photocleavage was observed for
1
(
λ
irr
>590 nm), whereas the complex is unreactive in the dark. This feature makes
1
a promising photodynamic therapy agent that does not operate via the production of singlet oxygen,
1
O
2
.