The ability to control the energy transfer in rare-earth ion-doped luminescent materials is very important for various related application areas such as color display, bio-labeling, and new light sources. Here, a phase-shaped femtosecond laser field is first proposed to control the transfer of multiphoton excited energy from Tm3+ to Yb3+ ions in co-doped glass ceramics. Tm3+ ions are first sensitized by femtosecond laser-induced multiphoton absorption, and then a highly efficient energy transfer