This paper describes the core-level electronic structure of La
1-xSr
xMnO
3 by laboratory x-ray photoelectron spectroscopy (Lab-XPS). For the first time, by Lab-XPS, we have succeeded in observing the shoulder structure in the lower binding energy side of Mn 2
p3/2 core-level spectra which has been observed only in the hard x-ray photoelectron spectroscopy (HX-PES). Then Mn
3+, Mn
4+, and the shoulder structure on the Mn 2
p3/2 are separated by a multi-peak analysis. The result of considering Mn
3+ ⁄ Mn
4+ ratio determined by the Sr fraction (x), it was found that a presence of intensity on Mn 2
p3/2 spectra other than the above. The peak was identified as the well-screened peak from the Mn
4+ sites, consequently the sum of the well-screened weight of the Mn
3+ sites and Mn
4+ sites was related to the electrical conductivity with x.
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