Pepper yellow leaf curl virus (PYLCV) is a threat to chili plants and can significantly reduce yields. This study aimed as a pilot project to detect PYLCV by analyzing compounds emitted by chili plants using gas chromatography-mass spectrometry (GC-MS). The samples investigated in this research were PYLCV-infected and PYLCV-undetected chili plants taken from commercial chili fields. The infection status was validated by using a polymerase chain reaction (PCR) test. A headspace technique was used to extract the volatile organic compounds emitted by plants. The analysis of GC-MS results began with pre-processing, analyzing sample compound variability with a boxplot analysis, and sample classification by using a multivariate technique. Unsupervised multivariate technique principal component analysis (PCA) was performed to discover whether GC-MS could identify PYLCV-infected or not. The results showed that PYLCV-infected and PYLCV-undetected chili plants could be differentiated, with a total percent variance of the first three principal components reaching 91.32%, and successfully discriminated between PYLCV-infected and PYLCV-undetected chili plants. However, more comprehensive studies are needed to find the potential biomarkers of the infected plants.