Low-temperature (40 K) photoluminescence (PL) measurements were used to follow the defect formation induced in the 4H-SiC epitaxial layer by irradiation with 200 keV H+ and 800 keV C+ in the fluence range of 5×109–3.5×1012 ions/cm2. After irradiation, the PL spectra show the formation of some sharp lines, called “alphabet lines”, located in the wavelength range of 425–443 nm, due to the recombination of excitons at structural defects induced by ion beams. The analysis of luminescence line intensity versus ion fluence allows us to mark two different groups of peaks, namely the P1 group (e, f and g lines) and the P2 group (a, b, c and d lines). The normalised yield of P1 group lines increases with ion fluence and reaches a maximum value, while the normalised yield of P2 group lines exhibits a threshold fluence and then increases until a saturation value is reached. These different trends indicate that, while the P1 group lines are related to the primary defects created by ion beams (interstitial defects, vacancies), the P2 group lines can be associated with some complex defects (divacancy, antisites). The trends are similar for irradiation with H+ and C+ ions; however, the defect formation occurs in the fluence range of 5×109–1011 ions/cm2 for C+ irradiation and 1011–4×1012 ions/cm2 for H+ irradiation. Taking into account the different values of energy deposited in elastic collision, a dependence on the ion type was found: the C+ ion results in being less effective in defect production as a higher defect recombination occurs inside its dense cascade.