In the framework of the simplest little Higgs model (SLHM), we perform a comprehensive study for the pair productions of the pseudoscalar boson η and SM-like Higgs boson h at LHC, namely gg(bb) → ηη, gg(qq) → ηh and gg(bb) → hh. These production processes provide a way to probe the couplings between Higgs bosons. We find that the cross section of gg → ηη always dominates over that of bb → ηη. When the Higgs boson h which mediates these two processes is on-shell, their cross sections can reach several thousand f b and several hundred f b, respectively. When the intermediate state h is off-shell, those two cross sections are reduced by two orders of magnitude, respectively. The cross sections of gg → ηh and qq → ηh are about in the same order of magnitude, which can reach O(10 2 f b) for a light η boson. Besides, compared with the SM prediction, the cross section of a pair of SM-like Higgs bosons production at LHC can be enhanced sizably. Finally, we briefly discuss the observable signatures of ηη, ηh and hh at the LHC, respectively.