The BSP chief alleged that people's faith in the EVMs had dwindled to a "worrisome level".
She described the idea of simultaneous Lok Sabha and Assembly polls as a ploy to divert attention from issues like poverty.
Mayawati's statement came hours before the all-party meeting called by Modi in the national capital to discuss several issues, including the idea of "one nation, one election", celebration of 150 years of Mahatma Gandhi's birth anniversary this year and 75 years of Independence in 2022.
In a statement, Mayawati said: "Elections in any democracy can never be a problem, nor the elections should be weighed from the point of view of expenditure and extravagance. The 'one nation, one election' is, in fact, an attempt to divert the attention from burning national issues such as poverty, inflation, unemployment and increase in violence, and is simply an illusion."
She further said that the stubbornness of conducting elections through electronic voting machines instead of ballot papers is the real threat to the democracy and Constitution of the country.
"In these circumstances, if the meeting was convened to deliberate upon the detrimental issue, then I would have definitely attended it," she added.
The "one nation, one election" was part of the Bhartiya Janata Party's (BJP) Lok Sabha election manifesto.
Last August, the Law Commission had recommended holding simultaneous elections to the Lok Sabha and state Assemblies to save public money.
In its draft recommendations, the commission had said simultaneous polls, with an exception of Jammu and Kashmir, would help the government of the day focus on "developmental activities rather than electioneering".
It, however, cautioned that holding simultaneous elections was not possible within the existing framework of the Constitution.
Last week, the Prime Minister called for widespread debate and consultations on simultaneous elections for the Lok Sabha and Vidhan Sabhas, keeping in view various aspects such as the resulting financial savings and consequent better utilization of resources.
( With inputs from IANS )