In superconducting materials, the characteristics of superconductivity appear when the temperature T is lowered below a critical temperature T_c. The value of this critical temperature varies from material to material. Conventional superconductors usually have critical temperatures ranging from around 20 K to less than 1 K. Solid mercury, for example, has a critical temperature of 4.2 K. As of 2009, the highest critical temperature found for a conventional superconductor is 39 K for magnesium diboride (MgB₂), although this material displays enough exotic properties that there is some doubt about classifying it as a "conventional" superconductor. Cuprate superconductors can have much higher critical temperatures: YBa₂Cu₃O₇, one of the first cuprate superconductors to be discovered, has a critical temperature of 92 K, and mercury-based cuprates have been found with critical temperatures in excess of 130 K. The explanation for these high critical temperatures remains unknown. Electron pairing due to phonon exchanges explains superconductivity in conventional superconductors, but it does not explain superconductivity in the newer superconductors that have a very high critical temperature.

Similarly, at a fixed temperature below the critical temperature, superconducting materials cease to superconduct when an external magnetic field is applied which is greater than the critical magnetic field. This is because the Gibbs free energy of the superconducting phase increases quadratically with the magnetic field while the free energy of the normal phase is roughly independent of the magnetic field. If the material superconducts in the absence of a field, then the superconducting phase free energy is lower than that of the normal phase and so for some finite value of the magnetic field (proportional to the square root of the difference of the free energies at zero magnetic field) the two free energies will be equal and a phase transition to the normal phase will occur. More generally, a higher temperature and a stronger magnetic field lead to a smaller fraction of the electrons in the superconducting band and consequently a longer London penetration depth of external magnetic fields and currents. The penetration depth becomes infinite at the phase transition.

The onset of superconductivity is accompanied by abrupt changes in various physical properties, which is the hallmark of a phase transition. For example, the electronic heat capacity is proportional to the temperature in the normal (non-superconducting) regime. At the superconducting transition, it suffers a discontinuous jump and thereafter ceases to be linear. At low temperatures, it varies instead as e^{−α /T} for some constant, α. This exponential behavior is one of the pieces of evidence for the existence of the energy gap.

The order of the superconducting phase transition was long a matter of debate. Experiments indicate that the transition is second-order, meaning there is no latent heat. However in the presence of an external magnetic field there is latent heat, because the superconducting phase has a lower entropy below the critical temperature than the normal phase. It has been experimentally demonstrated that, as a consequence, when the magnetic field is increased beyond the critical field, the resulting phase transition leads to a decrease in the temperature of the superconducting material.