The figure for pupils receiving the highest grade obtainable rose from 7.2% last year to 7.3% in 2014.
Overall, the number of subject entries dropped by 3.8% this year from 32,836 in 2013 to 31,600.
At A* - A there was a slight decrease of 0.8% percentage points from last year to 29.9%.
Entries achieving grades A* - C rose slightly to 83.7%.
There was little change in the overall A* - E pass rate at 98.1%. Last year, it was 98.2%.
The Sciences, Maths and Art and Design continue to be the best subjects for NI pupils.
For Mathematics, an impressive 45.3% of entries were awarded grades A* - A.
High performances were also recorded in modern language subjects and Further Maths, the latter of which 60.2% of entries here achieved A* - A.
The most popular A-Level subjects continue to be Biology, Mathematics, History, English and Religious Studies.
The most popular subject for boys is Maths, with 1,815 entries, while the top choice for girls is Biology with 1,871 entries.
Film and Media Studies saw a jump in entrant by 5.7% while and Art and Design rose 3.5%.
Anne Marie Duffy, Director of Qualifications at the Council for the Curriculum, Examinations and Assessment (CCEA), said: "On behalf of all the GCSE and GCE awarding bodies operating in Northern Ireland, I would like to offer my congratulations to students receiving results this morning.
"These excellent results reflect your hard work and dedication to study over the last two years," she said.
"In recognising the efforts of students, I must also pay tribute to the expertise of our teachers who have shared in your success today. Teachers hold a key role in ensuring that the examination system in Northern Ireland continues to run effectively.
It is notable that during a year when GCE entries dropped, the popularity of subjects that support the creative industries increased. It will be interesting to see if this becomes a trend over the next few years in response to the growing creative economy in Northern Ireland.
Anne Marie Duffy, CCEA
Meanwhile, a teachers' union said that the success of Northern Ireland's academic high-fliers only serves to highlight the disparity between them and the province's under-achievers.
Avril Hall-Callaghan, General Secretary of the Ulster Teachers' Union, said that while the region had some of the UK's best exam results, it also had some of the poorest.
"This disparity must be addressed or we risk losing a generation of young people who see little future for themselves," she said.
"There are arguably a number of reasons but the issue would be best addressed if policy makers took a holistic approach, particularly in terms of funding a child's learning journey from pre-school days into adulthood.
"The importance of early years and primary school education is long-established. Many would argue that the first two years of a baby's learning are crucial with experts telling us that 75% of brain development occurs between birth and the age of two.
"So it is imperative that children's education before Year One is handled by qualified teachers as this is such a vital time for a child's learning development and such a specialised area in teaching," she continued.
"Another issue is the disparity in funding between the primary and secondary sector."
In monetary terms primary schools here have one of the worst primary-secondary funding differentials in the UK. This is despite the fact that primary schools are now expected to deliver a wider range of subjects than ever due to the Revised Curriculum."
Avril Hall-Callaghan, Ulster Teachers' Union
Ms Hall-Callaghan said that Northern Ireland also has some of the highest pupil to teacher ratios in Europe.
"Children need smaller classes, not larger, if they are to fulfil their maximum potential. They need support and guidance from expert teaching, and they need that from the very start of their educational experience.
"Perhaps our policy makers should take a more holistic view of this year's exam results to see where the roots of our under-achievers lie."
NUS-USI President Rebecca Hall said that anyone unsure of their next steps should seek careers guidance about their education or career plans.
"If anyone did not receive the grades they wanted or they don't know what their future plans are, it is crucial that people seek careers guidance about potential next steps in their career or educational path.
"There are so many options and courses that are available and people should not be dispirited if they don't receive the grades that they were hoping to," she said.
Careers Service telephone: 0300 200 7820
"I would strongly encourage anyone who is unsure what their next move will be to contact a careers adviser at their education institution or contact to the Department for Employment and Learning's Careers Service and discuss potential opportunities."