Methane and its oxidation product (i.e., CO2) are both greenhouse gases. In the product chain of CO hydrogenation to hydrocarbon reaction, methane is also an unwanted product due to its poor added value. Herein we investigated the effect of structure‐directing agent urotropine on cobalt‐based catalyst supported on Al–O–Zn type carrier and achieved an initial and pioneering exploration of methane‐free CO hydrogenation to hydrocarbon reaction at mild CO conversion range. The catalyst modified by urotropine has a nanoflower micromorphology and can significantly change the reaction performance, almost completely eliminating the ability of the catalyst to inhibit C–C coupling within a mild CO conversion range, that is, it can produce no or less C1‐C4 gaseous hydrocarbons, while rich in condensed hydrocarbons (i.e., C5+ hydrocarbon selectivity can reach as high as 92.8%‐100.0%).