Monophasic CaFe5O7 ceramic has been synthesized by solid state route. Its microstructural features have been studied by diffraction techniques and electron microscopy images before and after Spark Plasma Sintering (SPS) annealings. This work is completed by measurements of electrical and thermal properties. Especially, attention is focused around the structural and electronic transition at 360 K for which specific heat measurements have revealed a sharp peak. Densification by SPS techniques led to a significant improvement of electrical conductivity above 360 K.