Let $S_N$ be the sum of vector-valued functions defined on a finite Markov chain. An analogue of the Bernstein--Hoeffding inequality is derived for the probability of large deviations of $S_N$ and relates the probability to the spectral gap of the Markov chain. Examples suggest that this inequality is better than alternative inequalities if the chain has a sufficiently large spectral gap and the function is high-dimensional.