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, $2Delta/k_{rm B}T_{rm c}=5.5$, is substantially smaller than the numbers reported for related compounds, implying a non-trivial relation between electronic dispersion and superconducting gap in iron arsenides.