The present invention discloses a hydrophobic-oleophilic and hollow fiber composite membrane and preparing method thereof. A preparing method includes preparing hollow tubular braids by two-dimensional braided technique using polyester filaments, wherein the hollow tubular braids are used as the reinforcements. The method further includes mixing polyvinylidene fluoride, hydrophobic pore-forming agent, and the rest of solvent to prepare a casting solution of surface separation layer. The method further includes pre-treatment processing of the reinforcements; and coating the casting solution of surface separation layer on the outer surface of the processed reinforcements through a spinning spinneret to form a primary membrane. The reinforcements are replaced by the primary after post-processing, and repeating the coating process.