Phosphorus (P) availability and loss risk are linked to P species; however, their alternations in the soil amended with biochar-blended organic fertilizer is not well known, particularly under contrasting soil properties and land management. In this study, the variance of soil P species extracted by sequential chemical extraction (SCE) and 31P NMR techniques, as well as the degree of P saturation (DPS), were investigated throughout three paddy and three vegetable fields. These fields were amended with three different fertilizers at the same P application rate: chemical fertilizer (CF), organic fertilizer substitution (sheep manure/biogas slurry, SM/BS), and biochar-blended organic fertilizer substitution (BSM/BBS). Results showed that the BSM/BBS and SM increased the total P contents by 7.5% and 5.9% (TP) and available P contents by 30.1% and 19.2% (AP), but decreased the DPS values by 19.4% and 11.7%, compared to the CF treatment. Yet, the BS decreased the TP and AP contents but increased the DPS values across the experimental sites. In the BSM/BBS amended soils, high AP contents were due to the increased inorganic P (NaHCO3-Pi), while the increased organic P (monoester and DNA) induced low DPS values and reduced soil P loss risk. Our study highlights that biochar-blended organic fertilizer is an effective agronomic way for improving P availability and decreasing P loss risk via the alteration of soil P species.