To design new mesoporous sucker-type selective sorbent for controlling environmental carcinogens like tobacco specific nitrosamines (TSNA), polyaniline (PANI) was controlled carefully to grow at different sites such as near the pore opening, in the channel or on the outside of SBA-15 by in one-pot synthetic and post-synthetic methods. The influences of aniline additional order, aniline to organosilicone ratio and with or without template are investigated in order to obtain the optimal growth position of PANI. Different location of PANI on SBA-15 was confirmed by TEM, N-2 adsorption-desorption characterization and zeta potential measurement. PANI grows preferentially in the channel and then near the pore orifice when proper amount aniline is added previous to silicon source. If aniline is added later after the silicon source, PANI will grow mainly on the outside surface of SBA-15. The location of PANI is in the pore entrances once the aniline is put into the solution after template is removed. Resulting composites realize different selectivity for TSNA and tobacco alkaloids. 1P-S15 production possesses a best TSNA adsorptive capacity (23.2%), higher than commercial activated carbon (15.5%). FTIR spectrum of TSNA in 1P-S15 and quantum calculations demonstrated that the adsorption of TSNA is controlled by hydrogen bonding.