High purity isobutylene streams are obtained by the hydroformylation of mixed butene streams containing butene-1 and isobutylene (and optionally butene-2) under conditions that hydroformylate primarily butene-1 to yield a mixture of valeraldehyde and isobutylene, which may be separated out as an enriched isobutylene stream and used in the production of methyl tertiary butyl ether, tertiary butyl alcohol, di-isobutylene or polyisobutylene.