A second generation poly(propylene amine) dendrimer (2) functionalised at the periphery with eight E-stilbene and eight 4-tert-butylbenzenesulfonyl units has been prepared. The absorption spectrum, fluorescence spectrum and decay, E ⇆ Z photoisomerization, and photocyclization of the Z-isomer of the stilbene units have been investigated in air equilibrated acetonitrile solutions. For comparison purposes, a reference compound of the peripheral dendrimer units, namely 4-tert-butyl-N-propyl-N-(4-styryl-benzyl)-benzenesulfonamide (1), has also been studied. The quantum yield of the E→Z photoisomerization reaction (0.30) and the fluorescence quantum yield of the E isomer (0.014) are substantially smaller for the units appended to the dendrimer compared to those of the reference compound 1 (0.50 and 0.046, respectively). The presence of a red tail and the biexponential decay of the emission band of the dendrimer indicate formation of excimers between the stilbene units appended at the poly(propylene amine) dendritic structure. Under the experimental conditions used (λ_exc = 313 nm), a Z/E photostationary state (around 9 ∶ 1 for both reference compound 1 and dendrimer 2) is reached in the time scale of minutes. On continuing irradiation, other photoreactions take place in the time scale of hours: the stilbene moiety of compound 1 undergoes photocyclization to phenanthrene (quantum yield 0.015), whereas in dendrimer 2 photocyclization to phenanthrene is accompanied by other processes, including a photoreaction involving the internal amine groups.