Two organo-bridged silsequioxanes derived from the same molecular precursor were synthesized with completely different local structure, namely long-range ordering. The photoluminescence features (emission, excitation, and time-resolved modes) were studied in the temperature range 13-300 K and compared with those of the molecular precursor. The effects of the self-assembling of the nanobuild blocks on these emission properties were discussed in terms of the magnitude of the hydrogen bonds between adjacent organic groups.