This paper is devoted to the study of operator-valued Triebel-Lizorkin spaces. We develop some Fourier multiplier theorems for square functions as our main tool, and then study the operator-valued Triebel-Lizorkin spaces on R d . As in the classical case, we connect these spaces with operator-valued local Hardy spaces via Bessel potentials. We show the lifting theorem, and get interpolation results for these spaces. We obtain Littlewood-Paley type, as well as the Lusin type square function characterizations in the general way. Finally, we establish smooth atomic decompositions for the operator-valued Triebel-Lizorkin spaces. These atomic decompositions play a key role in our recent study of mapping properties of pseudo-differential operators with operator-valued symbols.