Carbon nanotube (CNT) arrays show great promise in developing anisotropic thermal conductive composites for efficiently dissipating heat from high-power devices along thickness direction. However, CNT arrays are always grown on some substrates and liable to be deformed and broken into pieces during transfer and solution treatment. In the present study, we intentionally synthesized well-crystallized and large-diameter (~80 nm) multiwalled CNT (MWCNT) arrays by floating catalyst chemical vapor deposition (FCCVD) method. Such arrays provided high packing density and robust structure from collapse and crack formation during post solution treatment and therefore favored to maintain original thermal and electrical conductive paths. Under optimized condition, the CNT arrays can be transferred into flexible composite films. Furthermore, the composite film also exhibited excellent thermal conductivity at 8.2 W/(m·K) along thickness direction. Such robust, flexible, and highly thermal conductive composite film may enable some prospective applications in advanced thermal management.