We report the Rh(I)‐catalyzed chain‐growth polymerizations of propargylated monosaccharides to form π‐conjugated polyacetylene‐type products with the monosaccharide substituents attached to the polyacetylene backbone via short methylene spacers. The homopolymerization provides helically chiral linear polyacetylenes of Mw ~ 20,000 soluble in either water (monosaccharide substituents with free OH groups) or organic solvents (acetylated monosaccharide substituents). The methodology is established for the transformation of prepared chiral polymers into fibers (average diameter ~2.7 μm) taking advantage of the electrospinning technique. Copolymerization of propargylated monosaccharides with 1,3,5‐triethynylbenzene cross‐linker provides hyper‐cross‐linked polyacetylene networks with monosaccharide units content up to 46 wt.%, permanent micro/mesoporosity and SBET area up to 482 m2 g−1. The monosaccharide substituents of the networks serve as centers active in reversible isothermal adsorption of water vapor from the air. The achieved H2O capture capacity of 200 mg g−1 (298 K, RH = 90%) shows monosaccharides as promising (co)building blocks for the construction of porous materials effective in water harvesting from air.