Systems and methods are provided for forming alkylate from a tertiary alcohol feed. Olefins for the alkylation reaction can be generated from a portion of the tertiary alcohol feed. The tertiary alcohol feed can be obtained, for example, by selective oxidation to convert a portion of an isoparaffin-containing feed into alcohol, such as conversion of isobutane to t-butyl alcohol. The alcohol can then be converted to an alkene, such as conversion of t-butyl alcohol to isobutene, in the alkylation reaction environment in the presence of a solid acid catalyst. The solid acid catalyst can then facilitate dimerization of the alkenes (e.g. isobutene) to form C8+ olefins (e.g. isooctene). A catalyst having an MWW framework is an example of a suitable solid acid catalyst.