Kc~ and Kfl X-rays of calcium were produced by bombarding a thick calcium wafer with oxygen, helittm and hydrogen ions. These reactions produce a substantial amount of inner shell ionization. The K X-ray spectra contain X-ray lines from calcium which emanate from initial states with a varying degree of K or L shell vacancies. The initial configurations were assigned on the basis of Hartree-Fock-Slater calculated energies. Related intensity ratio of 1 s ~ 2p (Ks) transitions and of 1 s---> 3p (Kp) transitions of H plus Ca, He plus Ca and O plus Ca were obtained. In addition to observing many new transitions due to multiple K and/or multiple L shell vacancies, energy shifts relative to the H plus Ca spectrum were observed in the O plus Ca spectrum due to M shell vacancies.