This study explored differences in dental biofilm solids and fluid fluoride after ingestion of NaF or Na2FPO3 in milk or non-fluoridated milk. Eighteen volunteers ingested 1 mg fluoride in 200 mL of milk or 200 mL of non-fluoridated milk. Biofilm samples were collected at baseline, 30, 60, and 240 min and biofilm solids and fluid were micro-analyzed for fluoride. Analysis of variance was performed and the total delivery, retention, and clearance of fluoride to biofilm solids and fluid were estimated as the area under the curve between 0 and 240 min. No statistically significant differences were found for baseline values. Biofilm fluid fluoride values ranged from 0.11 ± 0.05 to 0.21 ± 0.08 µg F/mL while biofilm solid values ranged from 0.62 ± 0.39 to 1.75 ± 1.16 µg F/g. Biofilm fluid values were significantly lower at 60 min for Na2FPO3 in milk. Clearance profiles for biofilm fluid diverged after the initial 60 min. Na2FPO3 had a smaller area under the curve from 60 to 240 min than NaF. Results of this study indicate that the release and clearance of fluoride in biofilm vary among fluoridation compounds and that the concentrations in biofilm solids and fluid also vary and are not correlated to each other in many cases.