Poly(vinyl phosphate-b-styrene) (PVPP-b-PS) block copolymers were synthesized successfully from poly(vinyl alcohol-b-styrene) (PVA-b-PS) by reaction with phosphorus oxychloride and subsequent hydrolysis. The obtained block copolymers were slightly crosslinked, and were characterized by various analytical techniques. The total phosphorus content and the ratio of the differently bound phosphorus were obtained by both solid-state $^{31}P$ NMR and pH titration, but the results differed slightly. Characterization by energy dispersion X-ray analysis (EDS) or Rutherford back scattering (RBS), on the other hand, determined the total phosphorus contents, but the results were quite different from those by solid-state $^{31}P$ NMR.