We report a novel non-solution synthesis of ultrafine SnO2 nanoparticles within multiwall carbon nanotube (MWCNT) networks by pre-mixing tin(II) 2-ethylhexanoate (C16H30O4Sn) and MWCNTs and subsequently annealing in air at 350°C, at which decomposition and oxidation of tin(II) 2-ethylhexanoate readily went on without destroying the MWCNTs. The resultant SnO2 nanoparticles with average size of ∼5nm were well-distributed either on the surface of MWCNTs or within themselves-constructed networks. When used as anode materials in lithium ion batteries (LIBs), the SnO2-MWCNT nanocomposites showed superior electrochemical properties, delivering discharge capacities of 1144mAhg−1 at 100mAg−1 and 1022mAhg−1 at 200mAg−1 after 50 cycles, 685mAhg−1 at 500mAg−1 and 640mAhg−1 at 1000mAg−1 after 100 cycles. Moreover, the mixture of tin(II) 2-ethylhexanoate and MWCNTs can be directly used as paste for fabrication of binder-free SnO2-MWCNT composite electrodes by simply spreading the mixture on current collectors (ex. Ni foam) and annealing in air. The as-prepared SnO2-MWCNT-Ni composite electrode delivered a discharge capacity of 434mAhg−1 at 500mAg−1 after 200 cycles. Besides, the present non-solution synthetic strategy is promising for low-cost and large-scale fabrication of SnO2/CNTs nanocomposites as high-performance anodes for electrochemical energy-storage.