It is possible:
$$1/2+1/3+1/6=1$$
In general, you might want to read up on Egyptian fractions.
Any nonnegative rational number (in particular, any positive integer) can be expressed as a sum of distinct unit fractions. One way to do this is to proceed greedily: that is, to keep subtracting off the largest remaining unused unit fraction until your remainder is a unit fraction. For example, if we wanted to write $2$ in this way, we could notice that
$$
\sum_{i=2}^{10} \frac{1}{i} < 2 < \sum_{i=2}^{11} \frac{1}{i}
$$
so we can start by writing
$$
2 = \sum_{i=2}^{10} \frac{1}{i} + R_1
$$
for some remainder $R_1$.
Then, notice that the largest unit fraction that will "still fit" is $\frac{1}{15}$: that is,
$$
\frac{1}{15} < R_1 < \frac{1}{14}
$$
So our next approximation is
$$
2 = \sum_{i=2}^{10} \frac{1}{i} + \frac{1}{15} + R_2
$$
and, after some work, we find that $\frac{1}{230} < R_2 < \frac{1}{229}$.
So the next approximation after that is
$$
2 = \sum_{i=2}^{10} \frac{1}{i} + \frac{1}{15} + \frac{1}{230} + R_3
$$
and, this time, it turns out that $R_3$ itself is a unit fraction, $R_3=\frac{1}{57960}$. So that gives us our representation of $2$ as the sum of unit fractions:
$$
2 = \sum_{i=2}^{10} \frac{1}{i} + \frac{1}{15} + \frac{1}{230} + \frac{1}{57960}
$$
It turns out that if you do this procedure for any rational number, it always terminates (that is, eventually your remainder is always a unit fraction). The proof of this is sketched in the wikipedia article I linked to above; essentially, it boils down to showing that the numerators of the $R_i$ must decrease at each step — so there's no way this process could continue indefinitely.
On the other hand, this may not be the most efficient representation of your number as a sum of unit fractions (whether your measure of efficiency involves number of terms or size of denominators). The example Wikipedia gives is the fraction $\frac{5}{121}$, where this "greedy" method produces the sum
$$
\frac{5}{121}=\frac{1}{25}+\frac{1}{757}+\frac{1}{763309}+\frac{1}{873960180913}+\frac{1}{1527612795642093418846225}
$$
but in fact there's a much more compact representation:
$$
\frac{5}{121}=\frac{1}{33}+\frac{1}{121}+\frac{1}{363}
$$