The temperature of something is merely a measure of how much energy it has. This energy is mainly the kinetic energy of the atoms (or molecules) that make up this "something", which are whizzing about. Each of these atoms/molecules makes its own partial contribution to the total energy of the system. In a total vacuum there is, by definition, nothing in the system. Therefore, nothing to contribute any energy to the system. The temperature, therefore, would be zero Kelvin. Of course, it is impossible to create a total vacuum, so that temprature is only approachable though not achievable. However, as one evacuates a system, the temperature will decrease towards zero as the population of atoms/molecules decreases towards a total vacuum. These temperatures can be (and indeed have been) measured.
There is a standard experimental apparatus in O Level physics that incorporates a mechanical alarm clock inside a bell jar. The purpose is to demonstrate the need for air to transmit sound waves. As the bell jar is evacuated of air, the ringing alarm gets quieter and quieter. One could, if one wished, incorporate a thermometer into this apparatus to show that, as the vacuum increases, the temperature inside the bell jar does indeed decrease.