Double-polarization observables in the reaction $vec{e}p rightarrow evec{p}gamma{}$ have been measured at $Q^2=0.33 (GeV/c)^2$. The experiment was performed at the spectrometer setup of the A1 Collaboration using the 855 MeV polarized electron beam provided by the Mainz Microtron (MAMI) and a recoil proton polarimeter. From the double-polarization observables the structure function $P_{LT}^perp$ is extracted for the first time, with the value $(-15.4 pm 3.3 (stat.)^{+1.5}_{-2.4} (syst.)) GeV^{-2}$, using the low-energy theorem for Virtual Compton Sattering. This structure function provides a hitherto unmeasured linear combination of the generalized polarizabilities of the proton.