A flame photometric detector with a silicon photodiode assembly instead of a photomultiplier tube for sulfur detection was developed and evaluated. The photosensitive area of photodiode, the optical design, and band-pass filters, were optimized. It was found that the optimal photosensitive area of the photodiode was 100 (mm)2, and three focus lenses combined with a broad band-pass filter of 378/52 nm and a QB21 glass yielded the best result. This design fully utilized the wide emission spectrum of S2*, the response characteristics of silicon photodiode, and effective absorption of strong emission spectrums of OH* at wavelength around 310 nm by QB21 glass. The limits of detection for nine kinds of sulfur containing compounds were between 5.8 × 10−12 to 9.5 × 10−12 g s−1. This mode provided a linear response of 3 orders of magnitude for compounds being tested and a selectivity of sulfur over carbon of 105. It is demonstrated for the first time that the overall performance of the flame photometric detector integrated with a silicon photodiode assembly work at room temperature was comparable to a conventional detector coupled with a photomultiplier tube, with advantages of short equilibration time, robust to electromagnetic interference and vibration, and low cost. The new detector can find wide application in gas chromatography and on-line monitoring instruments for sulfur measurement.