Terpenoids not only are an important health factor in baijiu but also contribute to the elegance and finesse of baijiu, and actinomycetes act as an important source of terpenoids in baijiu. Four strains of actinomycetes- (SPQ1), (SPS1), (SPG1), and (SPH1)-obtained from the Daqu, pit mud, fermented grains and air, respectively, in the production of baijiu were used in solid-state and liquid fermentation with five brewing raw materials as the substrates. The terpenoids in the metabolites were analyzed and compared using gas chromatography-mass spectrometry (GC-MS). We found that the four strains of actinomycetes produced 31 terpenoids from the hydrolysates of five fermentation substrates during liquid fermentation, and the total terpenoid content was 989.94 μg/kg in the fermentation products. After 28 days of solid-state fermentation, the four actinomycete strains produced 64 terpenoids using the five fermentation substrates, and the total terpenoid content was 23,651.52 μg/kg in the fermentation products. The different fermentation substrates and fermentation methods have a great influence on the terpenoids produced by actinomycetes.