A measurement of the vector to pseudoscalar conversion decay ϕ→π0e+e− with the KLOE experiment is presented. A sample of ∼9500 signal events was selected from a data set of 1.7 fb−1 of e+e− collisions at collected at the DAΦNE e+e− collider. These events were used to perform the first measurement of the transition form factor |Fϕπ0(q2)| and a new measurement of the branching ratio of the decay: . The result improves significantly on previous measurements and is in agreement with theoretical predictions.