Target synthesis of metal-organic nanotubes (MONTs) through a classic "rolling-up" mechanism remains a big challenge for coordination chemists. In this work, we report three 2D lamellar compounds and one (4,0) zigzag MONT based on a common honeycomb coordination skeleton. Our synthetic strategy toward sheet/tube superstructure transformation is to asymmetrically modify the inter-layer interactions by gradually increasing the size of the amine templates. Eventually, to relieve the surface tension of individual layers and to enhance surface areas and optimize host-guest interactions to accommodate bigger guests, spontaneous rolling up to form a tubular structure was achieved. © 2013 American Chemical Society.