Pyroligneous acid (PA) is rich in bioactive compounds and known to have the potential to improve crop productivity and phytochemical content. However, the synergistic effect of PA and fertilizer has not been thoroughly studied. In this study, we assessed the biostimulatory effect of different rates of foliar PA application (i.e., 0, 0.25, 0.5, 1, and 2% PA/ddH2O (v/v)) combined with full rate (i.e., 0.63, 0.28, 1.03 g) and half rate of nitrogen-phosphorus-potassium (NPK) fertilizer on the yield and nutritional quality of greenhouse-grown tomato (Solanum lycopersicum ‘Scotia’). Plants treated with 0.25% and 0.5% PA showed a significantly (p < 0.001) higher maximum quantum efficiency of photosystem II (Fv/Fm) and increased potential photosynthetic capacity (Fv/Fo), especially when combined with the full NPK rate. Leaf chlorophyll was significantly (p < 0.001) increased by approximately 0.60 and 0.49 folds in plants treated with 2% PA and full NPK rate compared to no spray and water, respectively. Total number of fruits was significantly (p < 0.001) increased by approximately 0.56 folds with the 2% PA irrespective of the NPK rate. The combined 2% PA and full NPK rate enhanced total fruit weight and the number of marketable fruits. Similarly, fruit protein, sugar and 2,2-diphenyl-1-picrylhydrazyl (DPPH) activity were significantly (p < 0.001) enhanced by the combined 2% PA and full NPK rate. In contrast, the 0.5% PA combined with half NPK rate increased fruit carotenoid and phenolic contents while the 2% PA plus half NPK rate enhanced fruit flavonoid content. Generally, the synergistic effect of PA and NPK fertilizer increased fruit elemental composition. These showed that foliar application of 2% PA with full NPK rate is the best treatment combination that can be adopted as a novel strategy to increase the productivity and quality of tomato fruits. However, further study is required to investigate the molecular basis of PA biostimulatory effect on plants.