Looking back, no.

North Korea and the Soviets wanted a unified Korea under their regime. South Korea and the US wanted a unified country under their regime. While the Communists were popular, they were not a majority and had no hope of winning in a fair election. UN sponsored elections were boycotted by the North, so only South Korea had the UN sponsored elections in 1948. The North simply created their own government and the South created theirs.

Both Kim Il-sung and Syngman Rhee wanted to unify, but only on their terms - no compromise. Rhee was given very little in the way of weapons by the US because they feared, if properly armed, he would start a war to reunify. This led to the ROK being overwhelmed in June 1950 by vastly superior and well armed North Korean soldiers.

Furthermore, Kim and Rhee built their power on reunification and kicking out the occupiers - namely the USA. To this end, they both put down challenges to their rule through simple things such as assassination. In the south, Kim GU and Yeo Un-hyeong, the former provisional government President and the founder of the People's Republic of Korea, they were both a challenge to Rhee and they both were assassinated at convenient times for Rhee. In the north, Cho Mansik was the victim. Another moderate, he was placed under house arrest in 1946 and murdered around the outset of the war. Had these men been in power instead of Rhee or Kim, things could have been much different.

So, no, there was no peaceful path to reunification. By 1948, the Cold War was under way, the Chinese were turning Communist, the North refused to participate in an election they had little hope of winning, and both sides were ruled by dictators with no regard for human rights being supported by super powers that had no business or interest in being in Korea. All moderate leaders were purged, arrested, and murdered, leaving two idealogues in control.

This question, I think, holds a lot of speculation but there could have been a chance that it followed the path the divided Germany took. That's my belief both countries were split for basically the same reason, though East Germany was forced down its path and Korea seemed to have been led down its. Time will tell. Here's the story I picked up:

Following WW2, the Russians and American's occupied the Korean Pennisula after the Japanese occupied it during the war. Much like what happened in Germany, the onsedt of the Cold War led to a breakdown in talks between the West and the USSR and each side maintained their occupation plans. This polarized already existing political ideological differences that lead to attempts to unify ruined by Russian support of Kim Il Sung in the north and blocking the elections that should have created a unified government. The Americans in the South did much of the same thing when they backed Syngman Rhee.

While it seems, much as it is today, that unification is a top domestic policy in both Koreas, those polarized political ideologies of Socialism/Communism and Capitalism remained a huge sticking point. Neither wanted to capitulate to the other and as soon as the DPRK saw a chance to invade the South with Soviet support, they took the chance and started the Korean War.

source: http://www.investopedia.com/articles/investing/040515/why-north-korea-south-korea-are-separated.asp