In recent years several groups of researchers have succeeded in making samples of cold molecules, at temperatures below 1 K, and of ultracold molecules, at temperatures below 1 mK. We concentrate on the formation of Cs2 dimers. Starting with laser-cooled atoms, photoassociation forms molecules in an excited electronic state. Various mechanisms are presented for stabilizing these molecules by spontaneous emission into a bound level of the ground electronic state. The design of new formation schemes requires precise knowledge of molecular potential curves that is well beyond the accuracy of ab initio calculations. We show that analytical long-range potentials can be fitted on photoassociation spectra and yield, through the determination of the C3 long-range coefficient, a value of the radiative lifetime of the 6P3/2 cesium level with an unprecedented accuracy. For short-range potentials it is possible to avoid explicit calculations by using asymptotic methods that generalize to long-range molecules the quantum-defect concepts developed for Rydberg atoms. Considering two coupled channels, we show how generalized Lu–Fano plots can extract precise information from experimental spectra.