This paper reported a novel method for the determination of total phosphorus (TP) content in soil and sludge by a headspace gas chromatography (HS-GC) method. It was based on a reaction between the soluble phosphate in the digestion solution and calcium oxalate solid to form a calcium phosphate precipitate and release oxalate ions, which can react with permanganate to form carbon dioxide, which was then measured by HS-GC. The results showed the complete conversion of phosphate (meanwhile to free oxalate ions in calcium oxalate) in 15 min at 60 °C. The present method has good repeatability (RSD < 2.6%) and good accuracy (RD < 7.3%) compared to the reference method. Therefore, the present HS-GC method can become a more effective method for determining the TP content in soil and sludge samples.