Norfolk Terrier Orange was rushed for treatment after returning distressed from a walk in Windsor Great Park.
Vets were unable to identify the toxin and said the five-year-old pet could not be saved.
Queen’s granddaughter Bea, 30, then took the heartbreaking decision to put down Orange last month.
She is now “worried sick” that four other Norfolk Terriers that live with her and her parents could be in danger.
A friend said: “No one seems to know if the poison was a natural substance like a fungi, or if there is a dog-hating maniac on the loose.
"Obviously Beatrice is keeping a close eye on her other pets.”
Beatrice, dad Prince Andrew and his ex-wife Sarah Ferguson also keep terriers Jack and Cici, both ten, and Teddy and Ginger, four, at their Royal Lodge home in the park.
Bea saw in the New Year in Kenya with new boyfriend, Edoardo Mapelli Mozzi — a romance first revealed by The Sun on Sunday.
The pal added: “She’s loved up with Edo but couldn’t stop thinking about her dog. It’s very upsetting.”
In 2017 The Sun told how the Yorks fired their dog walker Amanda Severn over an affair with Andrew’s butler Terry Holdforth.
Later that year Orange went missing. Police, rangers, staff and friends searched Great Park for several days before the pet was found.
The pal added: “It’s hard to believe Orange would have wandered off twice, and been poisoned, if Amanda still had her job. She just hasn’t been replaced.”
Norfolk Terrier Max, a gift for Bea’s 13th birthday, disappeared for three weeks in 2008, with even the Queen joining the search.
In 2012 Max died of his injuries after he was attacked by corgis at Balmoral.
by Dr Nicola Robinson, Veterinary poisons Advice Service
ALGAE in stagnant water can seriously damage a dog’s nervous system.
Cherry laurel (a type of bush) can break down into cyanide. There would have to be very high levels in a pet for it to kill.
Other dangers include mould from a discarded sandwich or xylitol, a natural sweetener found in chewing gum.
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