The affective appraisal of odors is known to depend on their intensity (I), familiarity (F), detection threshold (T), and on the baseline affective state of the observer. However, the exact nature of these relations is still largely unknown. We therefore performed an observer experiment in which participants (N = 52) smelled 40 different odors (varying widely in hedonic valence) and reported the intensity, familiarity and their affective appraisal (valence and arousal: V and A) for each odor. Also, we measured the baseline affective state (valence and arousal: BV and BA) and odor detection threshold of the participants. Analyzing the results for pleasant and unpleasant odors separately, we obtained two models through network analysis. Several relations that have previously been reported in the literature also emerge in both models (the relations between F and I, F and V, I and A; I and V, BV and T). However, there are also relations that do not emerge (between BA and V, BV and I, and T and I) or that appear with a different polarity (the relation between F and A for pleasant odors). Intensity (I) has the largest impact on the affective appraisal of unpleasant odors, while F significantly contributes to the appraisal of pleasant odors. T is only affected by BV and has no effect on other variables. This study is a first step towards an integral study of the affective appraisal of odors through network analysis. Future studies should also include other factors that are known to influence odor appraisal, such as age, gender, personality, and culture.