Yes, and there is a simple algorithm to achieve this. First, we subtract successive reciprocal numbers $(1/1,\ 1/2,\ 1/3,\ \ldots)$ until the remainder is less than the next reciprocal number. This is always possible because the harmonic series is divergent.
If the remainder is zero then we are done, so let us assume that
$$0 < \frac{a}{b} < 1.$$
There exists a unique positive integer $m$, greater than any of the preceding denominators, so that
$$\frac{1}{m} \le \frac{a}{b} < \frac{1}{m-1}.$$
Therefore,
$$\frac{a}{b} - \frac{1}{m} = \frac{am-b}{bm} \ge 0.$$
But
$$\frac{a}{b} < \frac{1}{m-1} \implies am-a < b \implies am-b < a,$$
so the numerator has decreased.
If the process is repeated, then the remainder will eventually be zero, since the numerators cannot decrease forever. Therefore, every positive rational number can be represented as a sum of distinct reciprocal numbers.
Example: To write 11/4 as a sum of distinct unit fractions, we subtract as many successive unit fractions as possible, starting with 1.
$$\frac{11}{4} - \frac11 - \frac12 - \frac13 - \frac14 - \frac15 - \frac16 - \frac17 - \frac18 = \frac9{280}.$$
The remainder lies between $\frac1{32}$ and $\frac1{31}$, so we subtract $\frac1{32}$.
$$\frac{9}{280} - \frac{1}{32} = \frac{1}{1120}.$$
Since the result is a unit fraction, we are done.
$$\frac{11}4 = \frac11 + \frac12 + \frac13 + \frac14 + \frac15 + \frac16 + \frac17 + \frac18 + \frac1{32} + \frac1{1120}.$$
Thanks to Barry Cipra for pointing out an error in a previous version of this post.