The E0 transition depopulating the first-excited 0+ state in 24Mg has been observed for the first time, and the E0 transition strength determined by electron-positron pair and γ-ray spectroscopy measurements performed using the Super-e pair spectrometer. The E0 transition strength is ρ2×103=380(70). A two-state mixing model implies a deformation of the first-excited 0+ state of β2≈1 and a change in the mean-square charge radius of Δ〈r2〉≈1.9fm2, which suggests a significant shape change between the ground state and first-excited 0+ state in 24Mg. The observed E0 strength gives direct evidence of shape coexistence and superdeformation in 24Mg, bringing this nucleus into line with similar behaviour in nearby N=Z nuclei. This result agrees with recent theoretical work on the cluster nature of 24Mg and has potential ramifications for nuclear reactions of astrophysical importance.