Recent clinical studies have suggested that alkalinization of local anaesthetic agents may shorten the onset time and lengthen their duration of action. In clinical practice, sodium bicarbonate 1.4 and 4.2% are often added to local anaesthetic agents to obtain these effects. We evaluated pH changes of 4 local anaesthetic solutions commonly used for obstetrical epidural anaesthesia, in order to develop titration curves with sodium bicarbonate 1.4 and 4.2%. Local anaesthetic agents tested included lidocaine 2% and bupivacaine 0.25% with and without epinephrine. Each one was divided in 10 mL aliquots, and supplemented with 25 micrograms of sufentanil (1 mL). The pH measurement were made with a pH-meter P 500 with a combined electrode (TBC 12/HS) in the standard solution and after incremental addition of 0.5 mL of 1.4 or 4.2% sodium bicarbonate. The percentage of the free form of local anaesthetic was calculated for each step, using the Henderson-Hasselbalch equation. Results showed that alkalinization is not beneficial with epinephrine free solutions. Increasing volumes of sodium bicarbonate, buffered the acidic effect of sodium bisulfite present in solutions containing epinephrine, and increased the percentage of the free form of local anaesthetic to the level of epinephrine free solutions. From this pH point upwards, the gain is poor and precipitates are generated. This study suggests that 1 mL of 4.2% sodium bicarbonate for 10 mL of local anaesthetic solution is the best theorical choice for alkalinization of a local anaesthetic associated with epinephrine.