The homogeneous acetic acid synthesis-type Ru–Co–Li/N-methylpyrrolidone catalyst for CO and H2 transformations has been studied at moderately high pressures. For 1CO:2H2, low acetic acid selectivity has been observed, along with remarkable methyl acetate selectivity, the absence of aldehydes and ethyl acetate and sharp deviations from the Anderson-Schultz-Flory distribution for both alcaohols and long-chain hydrocarbons. For 1CO:1H2 and slightly elevated pressure, acetic acid selectivity slightly increased, notable ethyl acetate formation was detected, and both long-chain hydrocarbons and alcohols disappeared. Hypotheses are discussed about the direct parallel formation of all observed product groups (hydrocarbons, alcohols, esters, and acetic acid) and hydrocarbon chain growth limitations according to the formed Ru–Co cluster size in the presence of the aforementioned catalytic system.