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Germanium arsenide (GeAs) is a layered semiconductor with remarkably anisotropic physical, thermoelectric and optical properties, and a promising candidate for multifunctional devices based on in-plane polarization dependent response. Understanding the underlying mechanism of such devices requires the knowledge of GeAs electronic band structure and of the hot carrier dynamics in its conduction band, whose details are still unclear. In this work, we investigated the properties of occupied and photoexcited states of GeAs in energy-momentum space, by combining scanning tunneling spectroscopy (STS), angle-resolved photoemission spectroscopy (ARPES) and time-resolved ARPES. We found that, GeAs is an indirect gap semiconductor having an electronic gap of 0.8 eV, for which the conduction band minimum (CBM) is located at the Gamma point while the valence band maximum (VBM) is out of Gamma. A Stark broadening of the valence band is observed immediately after photoexcitation, which can be attributed to the effects of the electrical field at the surface induced by inhomogeneous screening. Moreover, the hot electrons relaxation time of 1.56 ps down to the CBM which is dominated from both inter-valley and intra-valley coupling. Besides their relevance for our understanding of GeAs, these findings present general interest for the design on high performance thermoelectric and optoelectronic devices based on 2D semiconductors.