Rhododendron latoucheae Franch. (R. latoucheae) is a valuable woody plant known for its high ornamental value. While purple flowers are a distinct and attractive variant phenotype of R. latoucheae, the underlying mechanism regulating its flower color is still poorly understood. To investigate the molecular regulatory mechanism responsible for the variation in flower color, we selected plants with white-pink and purple petals as the object and conducted analyses of metabolites, key genes, and transcription factors associated with flower color. A combined metabolome–transcriptome analysis was performed, and the expression of key genes was subsequently verified through qRT-PCR experiments. The results of our study demonstrated a significant enrichment of differential metabolites in the flavonoid metabolic pathway. Changes in anthocyanin content followed the same trend as the observed flower color variations, specifically showing significant correlations with the contents of malvidin-3-O-glucoside, dihydromyricetin, gallocatechin, and peonidin-3-O-glucoside. Furthermore, we identified three key structural genes (F3GT1, LAR, ANR) and four transcription factors (bHLH130, bHLH41, bHLH123, MYB4) that are potentially associated with the biosynthesis of flavonoid compounds, thereby influencing the appearance of purple flower color in R. latoucheae.