The most sensitive lines of carbon, used nowadays for its determination in steels by laser-induced-breakdown spectroscopy (LIBS), are at vacuum UV and, thereby, LIBS potential is significantly reduced. We suggested the use of the C I 833.51 nm line for carbon determination in low-alloy steels (c(C)~0.186-1.33 wt.%) in air. Double-pulse LIBS with the collinear scheme was performed for maximal enhancement of a carbon emission signal without substantial complication of experimental setup. Since this line is strongly broadened in laser plasma, it overlapped with the closest iron lines greatly. We implemented a PCR method for the construction of a multivariate calibration model under spectral interferences. The model provided a RMSECV = 0.045 wt.%. The predicted carbon content in the rail templet was in an agreement with the reference value obtained by a combustion analyzer within the relative error of 6%.