Accurate calibration of the Chandra Low Energy Transmission Grating (LETG) higher-order (|m|>1) diffraction efficiencies is vital for proper analysis of spectra obtained with the LETG's primary detector, the HRC-S, which lacks the energy resolution to distinguish different orders. Pre-flight ground calibration of the LETG was necessarily limited to sampling a relatively small subset of spectral orders and wavelengths, and virtually no higher-order data are available in the critical region between 6 and 10 Å. In this paper, we describe an analysis of diffraction efficiencies based on in-flight data obtained using the LETG's secondary detector, the ACIS-S. Using ACIS, the relative efficiency of each order can be studied out to |mλ| ~ 80 Å, which is nearly one-half of the LETG/HRC-S wavelength coverage. We find that the current models match our results well but can be improved, particularly for the even orders just longward of the Au-M edge at 6 Å.