An all-electron full configuration interaction (FCI) calculation of the adiabatic potential energy curves of some of the lower states of BeH molecule is presented. A moderately large ANO basis set of atomic natural orbitals (ANO) augmented with Rydberg functions has been used in order to describe the valence and Rydberg states and their interactions. The Rydberg set of ANOs has been placed on the Be at all bond distances. So, the basis set can be described as 4s3p2d1f/3s2p1d(Be/H)+4s4p2d(Be). The dipole moments of several states and transition dipole strengths from the ground state are also reported as a function of the RBe–H distance. The position and the number of states involved in several avoided crossings present in this system have been discussed. Spectroscopic parameters have been calculated from a number of the vibrational states that result from the adiabatic curves except for some states in which this would be completely nonsense, as it is the case for the very distorted curves of the 3s and 3p math states or the double-well potential of the 4p math state. The so-called “D complex” at 54 050 cm−1 (185.0 nm) is resolved into the three 3d substates (math,math,math). A diexcited valence state is calculated as the lowest state of math symmetry and its spectroscopic parameters are reported, as well as those of the 2 math (4d) state The adiabatic curve of the 4 math state shows a swallow well at large distances (around 4.1 Å) as a result of an avoided crossing with the 3 math state. The probability that some vibrational levels of this well could be populated is discussed within an approached Landau–Zerner model and is found to be high. No evidence is found of the E(4sσ) math state in the region of the “D complex”. Instead, the spectroscopic properties obtained from the (4sσ) 6 math adiabatic curve of the present work seem to agree with those of the experimental F(4pσ) math state. The FCI calculations provide benchmark results for other correlation models for the open-shell BeH system and evidence both the limitations and capabilities of the basis set.