One method mention by Anna V is to use X-ray Thomson Scattering, which is also known as Compton scattering. I figured I would expand on how this works.
When x-rays scatter off of stationary free electrons, relativistic energy and momentum conservation requires that the scattered photon is shifted to lower energy (longer wavelength). The shift is known as the Compton shift, and is given by $\Delta E = \hbar^2 q^2 / 2m$ where $q$ is the momentum transferred to the electron (which can be determined from the scattering angle).
However, the electrons in any material, and in particular an extremely hot, dense plasma, are not stationary. Instead they have some momentum distribution, which is determined by the electronic wavefunctions (property of the material) and by the temperature. Scattering off of a moving electron gives (again by energy and momentum conservation) $\Delta E = \hbar^2 q^2 / 2m + \hbar \vec{q} \cdot \vec{p}/m$, where $\vec{p}$ is the momentum of the electron before scattering.
This Doppler effect causes, for a constant incident x-ray energy, a broad down-shifted peak to be present in the scattered x-ray spectrum. The center is at the standard Compton shift, while the shape of the peak can be used to extract the electronic momentum distribution. From that it is possible to extract a temperature.