Polymer solar cells (PSCs) based on polymer donors and nonfullerene small molecule acceptors are a very attractive technology for solar energy conversion, and their performance is heavily determined by film morphology. It is of considerable interest to reveal instructive morphology–performance relationships of these blends. This feature article discusses the recent advances in analysing the morphology formation of nonfullerene PSCs with an effective polymer thermodynamic quantity, i.e., Flory–Huggins interaction parameter χ. In particular, guidelines of high and low χ systems are summarized. The fundamental understanding of χ and its correlations to film morphology and photovoltaic device parameters is of utmost relevance for providing essential material design criteria, establishing suitable morphology processing guidelines, and thus advancing the practical applications of PSCs based on nonfullerene acceptors.