The transient absorption spectra dynamics for hybrid associates of colloidal CdS quantum dots, passivated by thioglycolic acid (CdS/TGA QDs), and methylene blue cationic dye molecules (MB+) were studied by femtosecond spectroscopy. It was established that one of the main channels of relaxation of the CdS/TGA QDs excitation energy in hybrid associates based on CdS/TGA QDs and MB+ is a fast energy transfer to the reduced forms of MB+ (MBOH•, MB•) that are formed still at the synthesis stage of samples. This channel strongly competes with the resonant energy transfer from the centers of radiative recombination in quantum dots to MB+. Therefore, for hybrid associates based on QDs/TGA and methylene blue, there is no any noticeable signal of the transient absorption corresponding to the triplet state of MB+ dye, which is then known to be actively involved in charge transfer.