We present measurements of the positron two-dimensional angular correlation of annihilation radiation (2D-ACAR) in TTF-TCNQ. We report also theoretical simulations of the 2D-ACAR in which the electron wave functions were expressed as TTF or TCNQ molecular orbitals obtained from self-consistent quantum chemical calculations. The positron wave function was calculated taking the charge transfer from TTF to TCNQ as a parameter. The best agreement with the experiment is obtained for a charge transfer of 0.7 electrons from the TTF to the TCNQ molecules. This is larger than the value of 0.55 obtained from a study of the Kohn anomaly. We investigate also the shape and position of the Fermi surface and conclude that a simple planar Fermi surface is consistent with our measurements.