The spectroscopic properties of five spiro[2 H-1-benzopyran-2,2′-indoline] compounds containing a nitro group in the 6-position of the benzopyran moiety ( 1–5) were studied as a function of temperature in media of different polarity, e.g., methylcyclohexane, 2-methyltetrahydrofuran (MTHF), glycerol triacetate, and ethanol. UV excitation of a spiropyran at ambient temperature leads to a triplet state of the merocyanine ( 3t ∗) prior to population of the trans and cis isomers. The yields of formation of 3t ∗ and the merocyanine ground states decrease in a similar manner on decreasing the temperature. In highly viscous media, where the photochemical ring opening is suppressed, phosphorescence and the T-T absorption of the spiropyran could be detected: e.g., λ TT = 451 nm, τ T = 0.2 s for 3 (R-1′: CH 3, R-8: OCH 3) in MTHF at temperatures below 100 K. Upon excitation at 530 nm photosomerization into a less stable cis isomer occurs. The quantum yield is reduced on decreasing the temperature, whereas the yields of fluorescence and population of the 3t ∗ state increase in a similar manner. A semilogarithmic plot of the inverse triplet life-time vs 1 T shows two linear sections, indicating rotation about the CC bond in fluid solution and a strong increase in triplet life-time due to the hindrance of rotation at very high viscosities. The 3t ∗ state, which is an intermediate in the photocolouration is not directly involved in trans→ cis photoisomerization.