Graphene has shown great potential for ultra-high frequency electronics. However, using graphene in electronic devices creates a requirement for electrodes with low contact resistance. Thermal annealing is sometimes used to improve the performance of contact electrodes. However, high-temperature annealing may introduce additional doping or defects to graphene. Moreover, an extensive increase in temperature may damage electrodes by destroying the metal–graphene contact. In this work, we studied the effect of high-temperature annealing on graphene and nickel–graphene contacts. Annealing was done in the temperature range of 200–800 °C and the effect of the annealing temperature was observed by two and four-point probe resistance measurements and by Raman spectroscopy. We observed that the annealing of a graphene sample above 300 °C increased the level of doping, but did not always improve electrical contacts. Above 600 °C, the nickel–graphene contact started to degrade, while graphene survived even higher process temperatures.