The quantum theory of relativistic mechanics to deal with the scalar fields behavior in a curved space-time is represented by the Klein–Gordon equation. In this work, we will investigate the gravitationally bound states of massive and massless scalar fields around a Einstein–Yang–Mills–Higgs’s rotating black hole. After applying the standard separation of variables ansatz, we will show in detail how to obtain the novel exact solutions of the radial part of the governing Klein–Gordon equation and express the radial solution in terms of the Confluent Heun functions. By applying the bound state boundary conditions, the Confluent Heun functions are reduced to be polynomials that lead to energy quantization. We find that the scalar fields have complex-valued energy levels that indicate the decaying/growing bound states known as quasibound states. In the end, using the exact radial solution, we derive the radiation distribution function of the black hole’s outer horizon to obtain the equation of the Hawking temperature.