An iron-based metal–organic framework, [Fe(BTC)] (BTC: 1,3,5-benzenetricarboxylate) is an efficient catalyst in the ring opening of styrene oxide with alcohols and aniline under mild reaction conditions. Out of the various alcohols tested for ring opening of styrene oxide, methanol was found to be the most reactive in terms of percentage conversion and reactivity. The rate of the ring-opening reaction of styrene oxide decreases as the size of the alcohol is increased, suggesting the location of active sites in micropores. [Fe(BTC)] was a truly heterogeneous catalyst and could be reused without loss of activity. The analogous compound [Cu3(BTC)2] was also found to be effective, although with somewhat lower activity than [Fe(BTC)]. The present heterogeneous protocol is compared with a homogeneous catalyst to give an insight into the reaction mechanism.