Electronic structure of newly synthesized single crystals of calcium iron arsenide doped with sodium with Tc ranging from 33 to 14 K has been determined by angle-resolved photoemission spectroscopy (ARPES). The measured band dispersion is in general agreement with theoretical calculations, nonetheless implies absence of Fermi surface nesting at antiferromagnetic vector. A clearly developing below Tc strongly band-dependant superconducting gap has been revealed for samples with various doping levels. BCS ratio for optimal doping, 2∆/kBTc = 5.5, is substantially smaller than the numbers reported for related compounds, implying a non-trivial relation between electronic dispersion and superconducting gap in iron arsenides.Iron-based high temperature superconductors form an increasingly growing subject for investigation. Unlike other types of high-temperature superconductors, ironbased compounds can be synthesized in form of various crystals, exhibiting a large variety of electronic band structures, magnetic properties, superconducting order parameters, and electronic properties in general [1][2][3]. On the other hand, experimental difficulties, connected to the limitations of each particular technique, and complexity of the electronic interactions in iron-based materials hinder accurate and precise determination of the electronic structure in many cases. Thus, despite such abundance of possible forms of iron-based superconductors, the electronic spectrum, including both electronic band structure and superconducting gap function, has been thoroughly addressed experimentally only for holedoped BaFe 2 As 2 [4-9] and LiFeAs [10][11][12]. Available information at hand is still insufficient to tell, which features are generic to all iron-based high-T c s and responsible for the effective electron pairing.Here we report detailed studies of the electronic structure of newly synthesized large single crystals of Ca 1−x Na x Fe 2 As 2 (CNFA), with doping level, x, up to 0.7 and T c between 14 and 33 K. Angle-resolved photoemission spectroscopy (ARPES) measurements were performed at 1 3 end station at BESSY II synchrotron in Berlin [13,14]. The sample surface was prepared by cleaving, and was shown to be highly suitable for ARPES experiments: sharp spectral features and a pronounced superconducting transition at nominal T c were observed, offering possibility for detailed studies of the electronic band structure and superconducting gap distribution with high resolution.The Fermi surface (FS) of CNFA consists of a propeller-shaped structure at the Brillouin zone (BZ) corner, alike other hole-doped 122 compounds, and holelike FS sheets at the BZ center of increased size [see Fig. 1(a,b)].