Crystallographic, electronic, and energetic analyses of the (2,33) [or (2,3,3,3) in the standard Zhadanov notation] bar-shaped stacking fault, observed in as-grown 4H-SiC epitaxial layers, are presented. The defect has been identified by means of spatially resolved microphotoluminescence (μ-PL) measurements at different emission wavelengths, focusing on the emission peak at 0.3 eV below the conduction band. Low temperature μ-PL measurements have also been performed. The defect has been identified and characterized using high resolution transmission electron microscopy. Experimental results are correlated and validated by the calculations of the Kohn–Sham electronic band structure and the defect formation energy.