Laminated structure design is one of the significant factors that affect the physical and mechanical properties of laminated bamboo sliver lumber (LBSL). Eight patterns of assembly for 5-ply LBSL (LLLLL, LLVLL, LVLVL, LVVVL, LLV’LL, LV’LV’L, LVV’VL, and LV’VV’L) were prepared in this study; L represents one horizontal layer of the bamboo-sliver veneer, V represents the layer that is vertical to L, and V’ represents the layer at an angle of 45 ° to the L (or V). The objective of this study was to investigate the exclusive effect of the laminated structure design on the performance of the LBSL, rather than the multiple effect of the number of plies, chemical components, matter content, etc. The results indicated that the bending modulus of elasticity (MOE), bending modulus of rupture (MOR), impact strength, tensile strength, and compressive strength decreased with the decrease in number of layers of ply, for the following levels of L-ply: 5-L-ply (LLLLL), 4-L-ply (LLVLL, and LLV’LL), 3-L-ply (LVLVL, and LV’LV’L), and 2-L-ply (LVVVL, LVV’VL, and LV’VV’L). For the LBSL with the same number of L layers, those which had more V’ layers possessed better properties, due to the action of the parallel component of the force of the V’ layer. The values of absorption swelling rate, breaking strength, and displacement indicated that the LBSL with higher structural complexity achieved poorer underwater dimensional stability, but better single-bolted connection performance.