Methyl formate in its first torsionally excited state (vt=1 at 131 cm-1) is detected for the first time toward W51 e2. All transitions from excited methyl formate within the observed spectral range are actually detected (82 transitions) and no strong lines are missing. The column density of the excited state is comparable to that of the ground state. For a source size of 7 we find that Trot = 104 +/- 14 K and N = 9.4 +4.0/-2.8 x 10^16 cm-2 for the excited state and Trot = 176 +/- 24 K and N = 1.7 +.2/-.2 x 10^17 cm-2 for the ground state. Lines from ethyl cyanide in its two first excited states (vt=1, torsion mode at 212 cm-1) and (vb=1, CCN in-plane bending mode at 206 cm-1) are also present in the observed spectrum. However blending problems prevent a precise estimate of its abundance. With regard to the number of lines of excited methyl formate and ethyl cyanide detected in W51 e2, it appears that excited states of large molecules certainly account for a large number of unidentified lines in spectral survey of molecular clouds.