Designing an amine modified silica derived from coal fly ash (CFA) towards direct air CO2 capture (DAC) provides an economic way to manage increasing atmospheric CO2 concentration utilizing solid wastes. In this work, rod-like SBA-15 (SBA-15-R) and wheat-like SBA-15 (SBA-15-W) with distinct pore lengths are synthesized from CFA by controlling the synthesis conditions and then modified by PEI via the wet impregnation method. Their CO2 adsorption behaviors under sub-ambient conditions are investigated to explore their feasibility under aggressive conditions. The adsorbents with various silica morphologies exhibit distinctive CO2 adsorption performance under ambient and sub-ambient conditions. At 35°C under dry conditions, the CO2 adsorption capacity increases with amine loading. The CO2 adsorption capacity (qe) of SBA-15-W-PEI with long channels reaches the highest qe of 1.92 mmol/g with 70 wt.% PEI loading due to a large amount of strong chemisorption sites. Under the sub-ambient conditions (-20°C, 400 ppm), SBA-15-R-PEI30 with short channels having weaker CO2 diffusion resistance exhibits promising CO2 uptake of 0.83 mmol/g. These findings indicate that the ultra-dilute CO2 adsorption at ambient temperature requires an adsorbent with large amounts of adsorption sites, whereas the adsorbents for cold temperature application should reconcile amine loading with CO2 diffusion resistance inside pores. The co-adsorption of H2O and CO2 significantly improves CO2 capacity from 0.83 mmol/g and 1.92 mmol/g to 1.81 mmol/g and 3.48 mmol/g for SBA-15-R-PEI30 (-20°C, 400 ppm) and SBA-15-W-PEI70 (35°C, 400 ppm), respectively. Furthermore, the CFA derived SBA-15-PEI shows good cyclic stability during five consecutive TSA cycles. Preparing the amine silica adsorbents from coal fly ash potentially reduces the adsorbent cost of DAC devices. Moreover, the systematic exploration of amine silica adsorbents at a wide range of temperatures guides the design of high-performance CO2 adsorbents employed under various climatic conditions.