This paper presents a set of 42 satellite transition energies and 58 valence ionization potentials of full configuration interaction (FCI) quality for small molecular systems. These reference energies are computed using the configuration interaction with a perturbative selection made iteratively (CIPSI) method, following the protocol developed for the QUEST database. The accuracy of various approximation methods, including coupled-cluster (CC) hierarchies (CC2, CCSD, CC3, CCSDT, CC4, and CCSDTQ), and many-body Green's functions (GW, GF2, and T-matrix) for ionization potentials are analyzed. The results show that CCSDTQ provides the most accurate results, with errors below 0.03 eV for the 42 IPs of small molecules. The performance of various approximations is discussed, highlighting their limitations in correctly modeling satellite transitions. The study also includes results for several molecules, including water, ammonia, carbon monoxide, and boron fluoride, demonstrating the accuracy of the FCI reference values. The paper emphasizes the importance of accurate reference energies for benchmarking theoretical methods and highlights the challenges in modeling satellite transitions due to their high excitation degree compared to the neutral reference state. The results are compared with experimental data, showing good agreement for many of the satellite states. The study contributes to the development of more accurate theoretical methods for computing satellite energies and ionization potentials.This paper presents a set of 42 satellite transition energies and 58 valence ionization potentials of full configuration interaction (FCI) quality for small molecular systems. These reference energies are computed using the configuration interaction with a perturbative selection made iteratively (CIPSI) method, following the protocol developed for the QUEST database. The accuracy of various approximation methods, including coupled-cluster (CC) hierarchies (CC2, CCSD, CC3, CCSDT, CC4, and CCSDTQ), and many-body Green's functions (GW, GF2, and T-matrix) for ionization potentials are analyzed. The results show that CCSDTQ provides the most accurate results, with errors below 0.03 eV for the 42 IPs of small molecules. The performance of various approximations is discussed, highlighting their limitations in correctly modeling satellite transitions. The study also includes results for several molecules, including water, ammonia, carbon monoxide, and boron fluoride, demonstrating the accuracy of the FCI reference values. The paper emphasizes the importance of accurate reference energies for benchmarking theoretical methods and highlights the challenges in modeling satellite transitions due to their high excitation degree compared to the neutral reference state. The results are compared with experimental data, showing good agreement for many of the satellite states. The study contributes to the development of more accurate theoretical methods for computing satellite energies and ionization potentials.