Silver nanostructures deposited on glass showed luminescent blinking when excited at a high 442 nm irradiance. The irradiance required to photoactivate the silver, was dependent on the nature of the silver nanostructures. Silver fractal-like structures were found to be highly emissive, requiring only ≈30 W/cm2 for photoactivation as compared to silver island films and spin-coated silver colloids, which required a significantly higher irradiance, >100 W/cm2, to observe similar luminescent emission. In contrast to our recent findings for gold colloids, foci with different color blinking were also observed, with an increase in luminescence intensity as a function of time. We place these findings in context with recent work from our laboratory which employs these silver nanostructures for applications in metal-enhanced fluorescence, a relatively new phenomenon in fluorescence, whereby metallic particles, colloids, and fractal-like structures can modify the intrinsic radiative decay rate of close proximity fluorescent species. These effects are a consequence of localized changes in photonic mode density around the fluorophores, and we can now report are typically observed at significantly lower illumination intensities as compared to those required to photoactivate silver. Subsequently, our findings strongly suggest that the enhanced fluorescence emission of fluorophores positioned in close proximity to metallic silver structures is not due to either intrinsic silver blinking, or indeed the silver luminescence pumping the fluorophore. Further, the intrinsic luminescence properties of silver reported here, suggest a new class of luminescence probes and labels.