Lead-free Sr0.6Ca0.4TiO3 ceramic was prepared by solid-state reaction route. X-ray diffraction technique showed the phase purity and identified the orthorhombic perovskite structure. Scanning Electronic Microscopy observation evidenced homogeneous morphology and dense microstructure. Electrical conduction and dielectric relaxation mechanisms at high temperature have been studied by complex impedance measurement techniques over a wide range of frequencies and temperatures, from 100 Hz to 1 MHz and from 573 K to 783 K. Fitting of impedance measurements allowed us to study grains and grain boundaries electrical characteristics and their contribution to the conduction and dielectric relaxation processes in the ceramic. Electrical conduction in grains is due to oxygen vacancy jumps for temperatures below 733 K and to polarons above 763 K. Electrical DC conductivity in grains and grain boundaries is mainly due to oxygen vacancies. Impedance measurements and relaxation time distribution function calculations show non-Debye-type relaxation effects for both grains and grain boundaries.