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The core-level X-ray photoelectron emission spectra of the quasi-one dimensional spin 1/2 antiferromagnetic system Sr14-xCaxCu24O41 (x = 0, 3.5, 6, 7, 8.4) were measured. The main peak of Cu2P(3/2) was about 933.8 eV, and the full width of half maximum height was about 3.3 eV. Simulation of Cu2P(3/2) by XPSPEAK41 shows that the percents of Cu2+ and Cu3+ in Sr14Cu24O41 are 92.13% and 7.87%, no obvious change to Cu2p core-level is observed by the partial substituting Ca for Sr, and the average valence of Cu in this system is estimated to be 2.08. The main peak of O1s is about 531.0 eV, and the weak shoulder toward the low binding energy direction can be considered as the contribution of Ca-O bond. The binding energies of Ca2P(3/2) and Sr3d(5/2) indicate that their valence in this system are both +2, without mixed valence.