Rational design and self-assembly of nanostructured electrode materials for high-performance energy-storage devices is highly desirable but still challenging. Herein, we design and synthesize hierarchical porous nanocomposite architectures consisting of mesoporous NaTi2(PO4)3 (MNTP) nanocrystals (NCs) with a pore size of about 10 nm and multi-wall carbon nanotube (MWCNT) networks for high-performance sodium ion batteries (SIBs). Our strategy is based on the hetero-assembly of MWCNTs and nanostructured building units by utilizing the screening effect of electrostatic repulsion in a solution engineered ionic strength using highly soluble ammonium salt to form three-dimensional hierarchical assemblies of MWCNT networks and packed MNTP NCs. Subsequent freeze-drying and calcination convert the assemblies into robust hierarchical porous MWCNTs-threaded particles. Calcination of residual ammonium salt introduces nitrogen into the MWCNTs. Such nanoarchitecture enhances electron/ion conductivity and structural stability as anode materials for SIBs. The nanocomposite has high initial Coulombic efficiency of 99%, high rate capability of 74.0 mAhg−1 at 50C, as well as long-term cycling stability with capacity retention of 74.3 mAhg−1 after 2000 cycles with only 0.012% loss per cycle at 10C. The results provide a general and scalable hetero-assembly approach to different types of nanocomposites for high-performance energy storage devices such as LIBs and SIBs.