Surge in cocaine deaths helps push fatal drug poisonings to record high
Of those, 2,593 (69%) were classed as drug misuse deaths.
The figures, published by the Office for National Statistics (ONS), show there were 371 deaths involving cocaine - a rise of 16% on the figure recorded in 2015.
Statisticians identified a rise in the purity of cocaine as one possible explanation for the increase, which has been logged despite estimates of usage remaining broadly steady.
The ONS report cited a warning from the National Crime Agency that there was a "significant increase" in both crack and powder cocaine purity in 2016, including at user-level.
This "may partly explain the increase in deaths relating to cocaine", the paper added.
A study published earlier this year flagged up "unprecedented" purity levels for street cocaine.
The report from DrugWise identified a two-tier market, with prices of around £30 to £40 a gram at "pub dust" purity of roughly 40%, ranging up to approximately £80 for purity in excess of 70%.
Cocaine-related mortality rates have been increasing year on year, reaching a record high of 6.4 deaths per one million population, the ONS statistics show. The majority of fatalities occur in men aged 30 to 49.
Figures for cocaine-related deaths will include some where it was taken in the form of crack as evidence to distinguish the form of the drug taken - crack or powder- is rarely given on death certificates.
In contrast to cocaine, deaths linked to heroin and/or morphine remained stable last year - with 1,209 compared with 1,201 registered in 2015.
There were rises in deaths involving the powerful painkiller fentanyl (from 34 in 2015 to 58 in 2016), paracetamol (from 197 to 219) and new psychoactive substances (NPS) from 114 to 123).
NPS typically mimic "traditional" drugs such as cocaine, cannabis and ecstasy, and were widely known as "legal highs" before laws criminalising their production, distribution, sale and supply were introduced last year.
People aged 40 to 49 had the highest rate of drug misuse deaths in 2016, overtaking the 30-39 age group.
The highest mortality rate from drug misuse was in the North East with 77.4 deaths per one million population, while the lowest rate was in the East Midlands with 29.1 deaths per one million population.
The figures prompted criticism of the Government's drugs policy.
Martin Powell, of the Transform Drug Policy Foundation, described the Home Office's approach as "scandalous".
He said: "The Government must accept responsibility for record numbers of people dying from overdoses year after year.
"Other countries value the lives of vulnerable people who use drugs enough to implement and fund many measures proven to save lives, like decriminalising drug users, safer drug consumption rooms and prescribing heroin."
Rosanna O'Connor, of Public Health England, said: "It is tragic that we are still seeing an increase in people dying from drug misuse, particularly among older heroin users.
"Many of these deaths can be explained as the 'Trainspotting' generation, often with poor physical and mental health, sadly losing their battle with long-term addiction to drugs."
She said a large number of heroin deaths are among people not in treatment and called on services to increase their efforts to reach those most at risk.