Carbon structures comprising sp 1 chains (e.g., polyynes or cumulenes) can be synthesized by exploiting on-surface chemistry and molecular self-assembly of organic precursors, opening to the use of the full experimental and theoretical surface-science toolbox for their characterization. In particular, polarized near-edge X-ray absorption fine structure (NEXAFS) can be used to determine molecular adsorption angles and is here also suggested as a probe to discriminate sp 1 /sp 2 character in the structures. We present an ab initio study of the polarized NEXAFS spectrum of model and real sp 1 /sp 2 materials. Calculations are performed within density functional theory with plane waves and pseudopotentials, and spectra are computed by core-excited C potentials. We evaluate the dichroism in the spectrum for ideal carbynes and highlight the main differences relative to typical sp 2 systems. We then consider a mixed polymer alternating sp 1 C 4 units with sp 2 biphenyl groups, recently synthesized on Au(111), as well as other linear structures and two-dimensional networks, pointing out a spectral line shape specifically due to the the presence of linear C chains. Our study suggests that the measurements of polarized NEXAFS spectra could be used to distinctly fingerprint the presence of sp 1 hybridization in surface-grown C structures.