The synergistic effect of soot formation refers to the interaction between different fuels during soot forming processes, which results in higher soot formation than any individual fuels. The present study experimentally investigates the synergistic effect of soot formation in co-flow diffusion flames of propane/ethylene fuel mixtures. The total carbon mass flow rate of the propane/ethylene mixture was kept constant at 0.5 mg/s, and the propane carbon ratio (RC) was defined as the ratio of carbon mass flow rate of propane to the total carbon mass flow rate. The laser-induced incandescence (LII) and light extinction (LE) techniques were applied to measure the soot volume fractions (SVF) at pressures of 0.1–0.5 MPa. The results showed strong synergistic effect in propane/ethylene mixtures at atmospheric conditions; however, increasing pressure weakens the synergistic effect. The LII intensity contours showed that the soot formation zone extends when synergistic effect occurs at RC = 0.1 and 0.2 for 0.1 and 0.3 Mpa. The normalized peak SVF showed that synergistic effect monotonically becomes weak with increasing pressure from 0.1 to 0.3 Mpa; meanwhile, the it still stayed strong at 0.2 Mpa when using normalized maximum soot yield, and then turned to be weaker as pressure increases. Further comparison analysis of the SVF profiles between RC = 0 and 0.1 revealed that the synergistic effect occurs at the two-wing area of the sooty flame at low axial flame height, and then gradually becomes stronger with increasing axial flame height in the soot zone for 0.1–0.3 Mpa. To illustrate the pressure effects on synergistic soot formation, numerical analysis in homogeneous closed reactor was conducted and it was found that The PAHs formation competition between C3H3 pathway and HACA mechanism results in the different soot formation phenomenon of ethylene/propane flames.