A spectroscopic analysis of diatomic AlCa generated by laser vaporization of a 2:1 Al:Ca metal alloy followed by supersonic expansion has been completed using resonant two-photon ionization spectroscopy. Four excited electronic states have been identified and investigated in the energy region from 13 500 to 17 900 cm(-1). These are the [13.5] (2) Pi(r), the [15.8] (2) Sigma, the [17.0] (2) Delta(3/2)(?), and the [17.6] (2) Delta(3/2) states. From rotational analysis excited state bond lengths have been measured for three of the four excited states, and the ground state has been unambiguously determined as a (2) Pi(r) state with a weighted least squares value of the ground state bond length of r(o)(n) 3.1479 +/- 0.0010 Angstrom A. The ionization energy of the molecule has also been directly determined as 5.072+/-0.028 eV. Ab initio calculations for the potential energy curves of seven low-lying states of AlCa [X (2) Pi(r), 2 Sigma(+), 4 Sigma(-), (4) Pi(r), (2) Pi(r)(2), (2) Delta, and (2) Sigma(-)] and for the X (1) Sigma(+) ground electronic state of AlCa+ have been carried out. In agreement with experiment, (2) Pi, is calculated to be the ground electronic state of the neutral molecule. The dissociation energies of AlCa (X (2) Pi,) into Al(3s(2)3p(1),(2)p(0))+Ca(4s(2),S-1) and for AlCa+ (X (1) Sigma(+)) into Al+(3s(2),S-1)+Ca(4s(2),S-1) are calculated to be 0.47 and 1.50 eV, respectively. The excited (2) Sigma(+), (4) Sigma(-), (4) Pi(r), (2) Pi(r)(2), (2) Delta, and (2) Sigma(-) states are calculated to lie 0.2, 0.7, 0.7, 1.1, 1.1, and 1.1 eV above X 2 Pi(r), respectively, and the vertical and adiabatic ionization energies of AlCa have been calculated to be 5.03 and 4.97 eV, respectively.