Accessories such as joints and terminations represent weak points in HVDC cable systems. The DC field distribution is intimately dependent on the thermal conditions of the accessory and on material properties. Moreover, there is no available method to probe charge distribution in these conditions. In this work, the field distribution in non-stationary conditions, both thermally and electrically, is computed considering crosslinked polyethylene (XLPE) as cable insulation and different insulating materials (silicone, rubber, XLPE) for a 200 kV joint assembled in a same geometry. In the conditions used, i.e., temperatures up to 70 °C, and with the material properties considered, the dielectric time constant appears of the same order or longer than the thermal one and is of several hours. This indicates that both physical phenomena need to be considered for modelling the electric field distribution. Both the radial and the tangential field distributions are analysed, and focus is given on the field distribution under the stress cone on the ground side and near the central deflector on the high voltage side of the joint. We show that the position of the maximum field varies in time in a way that is not easy to anticipate. Under the cone, the smallest tangential field is obtained with the joint insulating material having the highest electrical conductivity. This results from a shift of the field towards the cable insulation in which the geometrical features produce a weaker axial component of the field. At the level of the central deflector, it is clear that the tangential field is higher when the mismatch between the conductivity of the two insulations is larger. In addition, the field grows as a function of time under stress. This work shows the need of precise data on materials conductivity and the need of probing field distribution in 3D.