sample() on a deque works fine in Python ≥3.5, and it's pretty fast.
In Python 3.4, you could use this instead, which runs about as fast:
sample_indices = sample(range(len(deq)), 50)
[deq[index] for index in sample_indices]
On my MacBook using Python 3.6.8, this solution is over 44 times faster than Eli Korvigo's solution. :)
I used a deque with 1 million items, and I sampled 50 items:
from random import sample
from collections import deque
deq = deque(maxlen=1000000)
for i in range(1000000):
    deq.append(i)
sample_indices = set(sample(range(len(deq)), 50))
%timeit [deq[i] for i in sample_indices]
1.68 ms ± 23.8 µs per loop (mean ± std. dev. of 7 runs, 1000 loops each)
%timeit sample(deq, 50)
1.94 ms ± 60.7 µs per loop (mean ± std. dev. of 7 runs, 100 loops each)
%timeit sample(range(len(deq)), 50)
44.9 µs ± 549 ns per loop (mean ± std. dev. of 7 runs, 10000 loops each)
%timeit [val for index, val in enumerate(deq) if index in sample_indices]
75.1 ms ± 410 µs per loop (mean ± std. dev. of 7 runs, 10 loops each)
That said, as others have pointed out, a deque is not well suited for random access. If you want to implement a replay memory, you could instead use a rotating list like this:
class ReplayMemory:
    def __init__(self, max_size):
        self.buffer = [None] * max_size
        self.max_size = max_size
        self.index = 0
        self.size = 0
    def append(self, obj):
        self.buffer[self.index] = obj
        self.size = min(self.size + 1, self.max_size)
        self.index = (self.index + 1) % self.max_size
    def sample(self, batch_size):
        indices = sample(range(self.size), batch_size)
        return [self.buffer[index] for index in indices]
With a million items, sampling 50 items is blazingly fast:
%timeit mem.sample(50)
#58 µs ± 691 ns per loop (mean ± std. dev. of 7 runs, 10000 loops each)