We report a photoionization and dissociative photoionization study of beta-alanine using IR laser desorption combined with synchrotron vacuum ultraviolet (VUV) photoionization mass spectrometry. Fragments at m/z = 45, 44,43, and 30 yielded from photoionization are assigned to NH3CH2CH2+, NH2CHCH3+, NH2CHCH2+, and NH2CH2+, respectively. Some new conformation-specific dissociation channels and corresponding dissociation energies for the observed fragments are established and determined with the help of ab initio G3B3 calculations and measurements of photoionization efficiency (PIE) spectra. The theoretical values are in fair agreement with the experimental results. Three low-lying conformers of the beta-alanine cation, including two gauche conformers G1+, G2+ and one anti conformer A+ are investigated by G3B3 calculations. The conformer G1+ (intramolecular hydrogen bonding N-H center dot center dot center dot O=C) is found to be another precursor in forming the NH3CH2CH2+ ion, which is complementary to the previously reported formation pathway that only occurs with the conformer G2+ (intramolecular hydrogen bonding G-H center dot center dot center dot N). Species NH2CHCH2+ may come from the contributions of G1+, G2+, and A+ via different dissociation pathways. The most abundant fragment ion, NH2CH2+, is formed from a direct C-C bond cleavage. Intramolecular hydrogen transfer processes dominate most of the fragmentation pathways of the beta-alanine cation.