We present the first measurement of a photoassociative spectrum of an alkaline earth element near the dissociation limit. The observed spectrum of Ca2 formed from cold atoms shows the regular vibrational series with the characteristic spacing of the 1/R3 asymptotic potential. The interpretation is in principle simplified compared to previous measurements on alkali metals by the nondegenerate ground state and the missing hyperfine structure of 40Ca. As an example, we derive the natural decay rate of the excited atomic 4p 1P1 state from the positions of the observed vibrational and rotational resonances with reduced uncertainty compared to previous measurements.