The globular cluster 47 Tuc exhibits a complex sub-giant branch (SGB) with a faint-SGB comprising only about the 10 per cent of the cluster mass and a bright-SGB hosting at least two distinct populations. We present a spectroscopic analysis of 62 SGB stars including 21 faint-SGB stars. We thus provide the first chemical analysis of the intriguing faint-SGB population and compare its abundances with those of the dominant populations. We have inferred abundances of Fe, representative light elements C, N, Na, and Al, α elements Mg and Si for individual stars. Oxygen has been obtained by co-adding spectra of stars on different sequences. In addition, we have analysed 12 stars along the two main RGBs of 47 Tuc. Our principal results are (i) star-to-star variations in C/N/Na among RGB and bright-SGB stars; (ii) substantial N and Na enhancements for the minor population corresponding to the faint-SGB; (iii) no high enrichment in C+N+O for faint-SGB stars. Specifically, the C+N+O of the faint-SGB is a factor of 1.1 higher than the bright-SGB, which, considering random (±1.3) plus systematic errors (±0.3), means that their C+N+O is consistent within observational uncertainties. However, a small C+N+O enrichment for the faint-SGB, similar to what predicted on theoretical ground, cannot be excluded. The N and Na enrichment of the faint-SGB qualitatively agrees with this population possibly being He-enhanced, as suggested by theory. The iron abundance of the bright and faint-SGB is the same to a level of ˜0.10 dex, and no other significant difference for the analysed elements has been detected.