Forensic pathologists are requested to select matrices alternative to blood in cases of toxicological interest in which blood is not available for different reasons. We evaluated morphine concentrations in blood, bile, and liver samples in 52 cases of heroin overdoses, relating them to each other, to understand the information that could be derived from their analysis. Gas chromatography/mass spectrometry analysis was performed for all the samples positive on screening for opiates. Shapiro-Wilk test, nonparametric Mann-Whitney test, linear regression analysis, and Bland-Altman test were used for analysis. Linear regression demonstrated that there was not a statistically significant association in morphine concentrations between blood and bile and blood and liver. Mean liver/blood ratio was 2.76, varying from 0.131 to 13.379, and bile/blood ratio was 28.79, varying from 0.28 to 559.16. According to these results, bile analysis is a "screening test"; biliary or hepatic concentration of morphine cannot provide information on hematic concentration at the time of death, having no forensic value taken individually.