The research status of dispersion, alignment and assembly of carbon nanotubes (CNTs)/polymer composite material is reviewed. In addition, the assembly and alignment in the arbitrary 3D space of multi-wall CNTs (MWNTs) are realized via the laser direct writing technique based on two-photon polymerization (TPP). The addition of thiol molecules makes the dispersion and doping concentration of CNTs in MWCNTs/polymer composites improved, and the optical and mechanical performances enhanced, and the fabrication of 3D CNTs functional devices realized. The research results indicate that, under the combination of TPP laser direct writing technique and thermal annealing process, the precise control of the orientation and placement of CNTs clusters can be achieved.