Their efforts came as the government said around 1,000 tonnes of the solidified oil had spilled from a cargo ship after a collision with another vessel near the Pearl River estuary in southern China Thursday.
It was the first time authorities had confirmed how much had been spilled.
Around 200 tonnes is likely to reach Hong Kong's shores, deputy environment chief Tse Chin-wan told reporters.
Thirteen of the city's most popular swimming spots are closed after white clumps of the oil started appearing Sunday.
But criticism of the government's response is mounting.
On Wednesday afternoon a team of local volunteers from Lamma Island in the south of Hong Kong braved sweltering heat and humidity to comb one of the worst-affected beaches, filling black bin bags with the lumps of oil.
A sour stench hung over the area and small numbers of dead fish were washing in.
The surrounding pathways were slippery with oil that had melted as temperatures hit 33 degrees Celsius (91 degrees Fahrenheit).
"The government should put in more effort to clean up. I'm here because no one else is doing it," Tony Mok, 31, told AFP.
Aleli Pena, 38, described the clean-up effort as "hard, hot and disgusting".
"We're all volunteers -- where are you government?" she asked.
Others said government cleaners had been working hard, but questioned why more had not been done to intercept the oil before it reached the beaches.
Environment campaigner Gary Stokes said the government should have installed pollution booms -- a kind of floating barrier -- to stop the oil reaching the beaches.
Tse had said earlier that he would not rule out the oil spreading to other areas.
The government has repeatedly described the palm oil as non-toxic and "harmless" to humans.
"You will see that many instant noodles have palm oil in them," Tse said Wednesday, although he acknowledged a large amount would affect the environment.
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