In this work, a series of microporous aminal-linked polymers (MALPs) are designed and prepared through the polycondensation of 1,4-bis(2,4-diamino-1,3,5-triazine)-benzene and four rigid tetra-aldehydes such as tetra(4-formylphenyl)methane, tetra(4-formylphenyl)silane, 1,3,5,7-tetra(4-formyphenyl)adamantane and 9,9′-spirobi[9H-fluorene]-2,2′,7,7′-tetracarboxaldehyde. Benefiting from highly contorted structural units introduced into the polymer network, the nitrogen-rich MALPs exhibit large surface areas (1093−1179 m 2 /g) and narrow pore size distributions (0.52, 0.93 nm), which endow them with superior small molecules adsorption performances such as CO 2 , toxic organic vapors, and volatile iodine. It is found that higher amounts of micropores greatly improve the small molecules adsorption performance. For example, among the prepared four MALPs, MALP-2 showed a largest adsorbed amount of 18.6 wt % CO 2 (273 K, 1 bar), and high adsorption selectivity of CO 2 /N 2 (22.5) and CO 2 /CH 4 (6.3). Notably, MALP-2 could uptake 35.4 wt % benzene, 30.7 wt % cyclohexane, 35.7 wt % toluene vapors even at 298 K and a very low-pressure of P/P 0 = 0.1, surpassing many other porous organic polymers. MALP-2 also displays an excellent iodine vapor adsorption capacity (218.5 wt %) and remarkable solution iodine adsorption ability. The stable physicochemical properties and excellent adsorption performances toward CO 2 , toxic organic vapor, and iodine demonstrate that MALPs are promising adsorbents for environmental remediation.