Bicyclo[n.2.0]alkan-1-ols are an integral part of various frameworks of natural products. The reaction of the lithium enolates of simple ketones with (ᩭphenyl vinyl sulfoxide and the controlled formation of bicyclo[n.2.0]alkan-1-ols was investigated. Facile access to bicyclo[n.2.0]alkan-1-ols (n = 3-6) bearing a bridgehead hydroxyl group was obtained. The ratio of bicyclo[n.2.0]alkan-1-ols (n = 3-6) to alkyated ketone was found to be dependent on enolate reactivity, electrophile conversion, time, reaction temperature, concentration, as well as the stability and steric strain observed in the final bicyclo[n.2.0]alkan-1-ol product.