In the Industry 4.0 scenario, innovation emerges as a clear driver for the economic development of societies. This effect is particularly true for the least developed countries. Nevertheless, there is a lack of studies that analyze this phenomenon in these nations. In this context, this study aims to examine the impact of perceived barriers to innovation to predict companies′ innovative intentions in an emerging economy. This study is a preliminary effort to use data mining and symmetry-based learning concepts, especially classification, to assist the identification of strategies to incentivize intention to innovate in companies. Using the decision tree classification technique, we analyzed a sample of Chilean companies (N = 5876). The sample was divided into large enterprises (LEs) and small and medium enterprises (SMEs). In the group of large companies, the barriers that most impact the intention to innovate are innovation cost, lack of demand innovations, and lack of qualified personnel. Alternatively, in the group of small-medium companies, the barriers that most impact the intention to innovate are lack of own funds, lack of demand innovations, and lack of information about technology. These results show how the perceptions of barriers are significant to predict the intentions of innovation in Chilean companies. Furthermore, the perceptions of these barriers are contingent on the organizational sizes. These findings contribute to understanding the effect of contingencies on innovative intention in an emerging economy.